Hydroprocessing catalysts and their production

ABSTRACT

Described herein is a catalyst precursor composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a reaction product formed from (i) a first organic compound containing at least one amine group and at least 10 carbon atoms or (ii) a second organic compound containing at least one carboxylic acid group and at least 10 carbon atoms, but not both, wherein the reaction product contains additional unsaturated carbon atoms, relative to the first or second organic compound, wherein the metals of the catalyst precursor composition are arranged in a crystal lattice, and wherein the reaction product is not located within the crystal lattice. A process for preparing the catalyst precursor composition is also described, as is sulfiding the catalyst precursor composition to form a hydroprocessing catalyst.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application claims the benefit of Provisional U.S. Application No.61/350,234, filed Jun. 1, 2010, the contents of which are herebyincorporated by reference herein.

FIELD

The invention relates generally to hydroprocessing catalysts and theirproduction.

BACKGROUND

At the same time as environmental regulations are mandating lower levelsof sulfur and nitrogen in distillate fuels, refineries are being forcedto process crude oils with larger amounts of these heteroatoms. Inaddition, residual S- and/or N-containing molecules can poison metal oracid sites on catalysts used downstream of a hydroprocessing process,such as in hydrocrackers. A need therefore exists to find catalystswhich will do more efficient desulfurization and/or denitrogenation,particularly when existing hydroprocessing units are limited in theirpressure capability.

Hydroprocessing catalysts usually comprise a sulfided Group 6 metal withone or more Group 8 to 10 metals as promoters on a refractory support,such as alumina. Bulk, unsupported catalysts are also known.Hydroprocessing catalysts that are particularly suitable forhydrodesulfurization, as well as hydrodenitrogenation, generallycomprise molybdenum or tungsten sulfide promoted with a metal such ascobalt, nickel, iron, or a combination thereof. These sulfided catalystsgenerally have a layered or platelet morphology.

The ability to modify the nanostructural morphology of hydroprocessingcatalysts appears to provide a possible way to control their activityand selectivity. Thus one of the important thrusts in hydroprocessingcatalyst research appears to be the realization that a key synthesistool for modifying nanostructure involves the incorporation of carboninto the sulfide structure. For example, U.S. Pat. No. 4,528,089 teachesthat the use of carbon-containing catalyst precursors gives more activecatalysts than catalysts prepared from sulfide precursors withoutorganic groups. Use of organic impregnation aids in preparing oxidecatalyst precursors has also been studied for some time (Kotter, M.;Riekeft, L.; Weyland, F.; Studies in Surface Science and Catalysis(1983), 16 (Prep. Catal. 3), 521-30, and U.S. Pat. No. 3,975,302).

In U.S. Pat. No. 7,591,942, it was demonstrated that sulfiding a bulkbimetallic Ni (or Co)/Mo (or W) phase containing a surfactant amine(located within the crystalline lattice of the oxide phase) with abackbone containing at least 10 carbon atoms gave a catalyst comprisingstacked layers of MoS₂ (or WS₂) having a reduced number of stacks ascompared to that obtained by sulfiding the carbon-free bulk oxide. Asimilar result was reported for bulk ternary Ni—Mo—W catalysts in U.S.Pat. No. 7,544,632. Lower number of stacks are important, since they mayimply the presence of smaller crystals of Mo/W sulfides, which in turncan result in a larger surface area available for catalysis.

U.S. Published Patent Application No. 2007/0072765 discloses a methodfor preparing a catalyst composition, which method comprises: (a)impregnating an inorganic catalyst support with an aqueous solutioncontaining (i) a salt of a Group VIII metal selected from Co and Ni,(ii) a salt of a Group VI metal selected from Mo and W, and (iii) aneffective amount of an organic agent selected from amino alcohols andamino acids; (b) drying the impregnated catalyst support to removesubstantially all water, thereby resulting in a metal-organic componenton support catalyst precursor; (c) calcining the substantially driedcatalyst precursor in the presence of an oxygen-containing atmosphereunder conditions to oxidize at least 30%, but not all, of the organicagent and produce a partially oxidized catalyst precursor containingcarbon; and (d) sulfiding the partially oxidized catalyst precursor inthe presence of a sulfiding agent to produce a sulfided catalystcomposition. Again the sulfide catalyst composition is found to have alower number of stacks than equivalent compositions produced withoutorganics present in the precursor.

Other potentially relevant publications can include, but are not limitedto, U.S. Pat. Nos. 6,989,348 and 6,280,610, European Patent Nos.0601722, 1041133, and 0181035, and International Publication Nos. WO96/41848, WO 95/31280, WO 00/41810, and WO 00/41811.

Although, reducing number of stacks can be important in increasingcatalyst surface area, it is not, in itself, sufficient to maximizecatalyst activity, since it does not necessarily ensure that thepromoter atoms (e.g., Co, Ni) are properly located on the sulfidestacks. According to the present invention, a new bulk mixed metal oxidecatalyst precursor composition is provided which, when sulfided, notonly reduces the number of stacks of the sulfided product but alsoenhances the efficiency of the promoter metal, thereby resulting in acatalyst of improved hydroprocessing activity.

SUMMARY

As refineries are being forced to process crudes with larger amounts ofsulfur and nitrogen, while at the same time environmental regulationsare mandating lower levels of these heteroatoms in products, a needexists to synthesize catalysts that can do more efficientdesulfurization and denitrogenation, particularly where existing unitsare limited in their pressure capability and/or more refractory feedsare desirable from a cost perspective. Since residual sulfur- and/ornitrogen-containing molecules can poison metal or acid sites oncatalysts used downstream of the hydrotreating process (such as inhydrocrackers), improvements in the hydroprocessing feed pretreatment(e.g., to FCC and/or hydrocracking units) can have a large impact on howacid and/or metal catalysts operate. Alumina-supported Ni orNi/Co-promoted molybdenum sulfides are the traditional catalysts usedfor hydrodenitrogenation (HDN) or hydrodesulfurization (HDS) atintermediate and relatively high pressures, and alumina-supportedCo-promoted molybdenum sulfides are the traditional catalysts for HDS atrelatively low pressures.

Improved modeling efforts have been underway worldwide to betterunderstand the complex structure sensitivity of these metal sulfidecatalysts. From a synthetic perspective, learning how to systematicallycontrol metal sulfide morphology remains a huge scientific andcritically important technological challenge. For the layered structuresof Group 6 (e.g., Mo and/or W) sulfides, this can involve considerationssuch as controlling lateral dimension, number of stacks in acrystallite, and properly siting the promoter atoms on the Group 6sulfide stacks.

It is important to note that lower number of stacks, by itself, doesgenerally indicate smaller sulfide crystallites, but it does not insurethat the promoter atoms (Co or Ni) are properly located. It had beenpreviously observed that substitution of a variety of inorganiccomponents into a Group 6/Groups 8-10 (e.g., NiMo, NiMoW, and/or NiW)oxide precursor did not significantly change the nanostructure of theresulting bulk sulfide catalysts. Although bulk NiMoW catalysts performhydroprocessing reactions well at relatively high pressures, there isstill an opportunity to develop improved catalysts.

One advantage of incorporating organics in the preparation of theprecursor according to the present invention can be that the density ofthe precursor tends to be substantially higher than when the organic isincorporated into the structure (whether crystalline or amorphous) ofthe oxide phase forming an oxide-organic hybrid. Without being bound bytheory, when an oxide-organic hybrid phase is formed, the organic cantake up “space” in the lattice of the hybrid phases, in some casesdrastically reducing the density relative to the mixed metal oxideand/or further limiting the relative amount of inorganic constituentspresent in the phase. In most of the preparations described herein, theorganic component is believed to be located in what were the empty porespaces of the oxide phase, leaving the high density of the oxide phasesubstantially intact, and/or to be coordinated to the surface (—OH)groups of the oxide phase. Nonetheless the presence of certain organiccompounds can significantly impact the crystallite size of sulfidesgenerated from the precursors seen by the reduction in the number ofstacks. Again without being bound by theory, an additional or alternateadvantage of the processes of the present invention can be that thepromoter metals from Groups 8-10 (e.g., Ni) appear to situate very wellin respect to the host Group 6 sulfide phase.

Accordingly, one aspect of the present invention relates to a catalystprecursor composition comprising at least one metal from Group 6 of thePeriodic Table of the Elements, at least one metal from Groups 8-10 ofthe Periodic Table of the Elements, and a reaction product formed from(i) a first organic compound containing at least one amine group and atleast 10 carbons or (ii) a second organic compound containing at leastone carboxylic acid group and at least 10 carbons, but not both (i) and(ii), wherein the reaction product contains additional unsaturatedcarbon atoms, relative to (i) the first organic compound or (ii) thesecond organic compound, wherein the metals of the catalyst precursorcomposition are arranged in a crystal lattice, and wherein the reactionproduct is not located within the crystal lattice. This catalystprecursor composition can be a bulk metal catalyst precursor compositionor a supported metal catalyst precursor composition. When it is a bulkmixed metal catalyst precursor composition, the reaction product can beobtained by heating the composition (though specifically theamine-containing compound or the carboxylic acid-containing compound) toa temperature from about 195° C. to about 250° C. for a time sufficientfor the first or second organic compounds to react to form additional insitu unsaturated carbon atoms not present in the first or second organiccompounds, but not for so long that more than 50% by weight of the firstor second organic compound is volatilized, thereby forming a catalystprecursor composition containing in situ formed unsaturated carbonatoms. Accordingly, a bulk mixed metal hydroprocessing catalystcomposition can be produced from this bulk mixed metal catalystprecursor composition by sulfiding it under sufficient sulfidationconditions, which sulfidation should begin in the presence of the insitu amide (i.e., the amide should be substantially present, or notsignificantly decomposed, by the beginning of the sulfiding step).

Another aspect of the present invention relates to a process forproducing a catalyst precursor composition containing in situ formedunsaturated carbon atoms, the process comprising: (a) treating acatalyst precursor composition comprising at least one metal from Group6 of the Periodic Table of the Elements, at least one metal from Groups8-10 of the Periodic Table of the Elements, with a first organiccompound containing at least one amine group and at least 10 carbonatoms or a second organic compound containing at least one carboxylicacid group and at least 10 carbon atoms, to form an organically treatedprecursor catalyst composition; and (b) heating said organically treatedprecursor catalyst composition at a temperature from about 195° C. toabout 250° C. for a time sufficient for the first or second organiccompounds to react to form additional in situ unsaturated carbon atomsnot present in the first or second organic compounds, but not for solong that more than 50% by weight of the first or second organiccompound is volatilized, thereby forming a catalyst precursorcomposition containing in situ formed unsaturated carbon atoms. Thisprocess can be used to make a bulk metal catalyst precursor compositionor a supported metal catalyst precursor composition. When used to make abulk mixed metal catalyst precursor composition, catalyst precursorcomposition containing in situ formed unsaturated carbon atoms can, inone embodiment, consist essentially of the reaction product, an oxideform of the at least one metal from Group 6, an oxide form of the atleast one metal from Groups 8-10, and optionally about 20 wt % or lessof a binder.

Still another aspect of the present invention relates to a process forproducing a sulfided hydroprocessing catalyst composition, whichcomprising sulfiding the catalyst precursor composition containing insitu formed unsaturated carbon atoms made according to any of theaforementioned processes described above or sulfiding any of thecatalyst precursor compositions described above under sulfidationconditions sufficient to produce the sulfided hydroprocessing catalystcomposition.

In an embodiment of any of the compositions and/or processes describedabove, the at least one metal from Group 6 can be Mo and/or W, and theat least one metal from Groups 8-10 can be Co and/or Ni. In anotherembodiment of any of the compositions and/or processes described above,the catalyst precursor composition can further comprise at least onemetal from Group 5 of the Periodic Table of the Elements, for example Vand/or Nb.

In an embodiment of any of the compositions and/or processes describedabove, the first organic compound comprise a primary monoamine havingfrom 10 to 30 carbon atoms and/or the second organic compound cancomprise only one carboxylic acid group and can have from 10 to 30carbon atoms.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an X-ray diffraction pattern of as-synthesized and driedhexagonal NiWO₄ catalyst precursor, produced according to ComparativeExample 1.

FIG. 2 shows an X-ray diffraction pattern of as-synthesized and driedNiWO₄(1,2-diaminocyclohexane)₂ catalyst precursor, produced according toExample 1.

FIG. 3 shows an X-ray diffraction pattern of as-synthesized and driedNiWO₄(ethylenediamine)₃ catalyst precursor, produced according toExample 2.

FIG. 4 shows X-ray diffraction patterns of the NiWO₄ catalyst precursorof Comparative Example 1, the NiWO₄(ethylenediamine)₃ catalyst precursorof Example 2, and the NiWO₄/(en)₁ and NiWO₄/(en)₁/citric acid_(0.33)catalyst precursors of Example 3.

FIG. 5 shows X-ray diffraction patterns of the sulfided NiWO₄ catalystof Comparative Example 1, as well as sulfided NiWO₄/(en)₁, sulfidedNiWO₄/(en)₁/citric acid_(0.33), and sulfided NiWO₄/citric acid_(0.33)catalysts of Example 3, with and without prior N₂ treatment at about320° C.

FIG. 6 shows X-ray diffraction patterns of the sulfidedNiWO₄/(en)₁/citric acid_(0.33) catalyst of Example 3 and sulfidedNiWO₄/citric acid_(0.33)/(en)₁ and sulfided NiWO₄/citric acid_(0.33)plus (en)₁ catalysts of Example 4.

FIG. 7 shows X-ray diffraction patterns of sulfided catalysts preparedfrom the amine and organic acid impregnated NiWO₄ precursors of Example5.

FIG. 8 compares X-ray diffraction patterns of theNiW_(0.975)Nb_(0.025)O₄ catalyst precursor produced according to Example6 and the NiWO₄ catalyst precursor produced according to ComparativeExample 1.

FIG. 9 compares X-ray diffraction patterns of the CoW_(0.5)V_(0.5)O₄catalyst precursor produced according to Example 7 and the NiWO₄catalyst precursor produced according to Comparative Example 1.

FIG. 10 represents a graph of relative hydrodenitrogenation activityagainst time on stream for certain Example 5 catalysts, compared to theactivity of a reference catalyst.

FIG. 11 represents x-ray diffraction spectra of Catalysts A and C—Ffollowing sulfidation in H₂S/H₂.

FIG. 12 shows amide formation and decomposition in air and nitrogen forcatalyst precursors treated in a similar manner to Catalysts E and F.

FIG. 13 shows x-ray diffraction spectra for a variety ofcobalt-containing catalyst precursor oxides.

FIG. 14 shows x-ray diffraction spectra for NiW- and NiMoW-containingcatalyst precursor oxides, with and without organic treatments.

FIG. 15 shows ¹³C NMR spectra for bulk catalysts having undergonetreatments using two organic compounds at various temperatures and undervarious conditions.

FIGS. 16A-B show infrared data characterizing bulk catalysts havingundergone treatments using two organic compounds at various temperaturesand under various conditions.

DETAILED DESCRIPTION OF THE EMBODIMENTS

One aspect of the present invention described herein relates to acatalyst precursor composition comprising at least one metal from Group6 of the Periodic Table of the Elements, at least one metal from Groups8-10 of the Periodic Table of the Elements, and a reaction productformed from (i) a first organic compound containing at least one aminegroup, or (ii) a second organic compound separate from said firstorganic compound and containing at least one carboxylic acid group, butnot both (i) and (ii). When this reaction product contains additionalunsaturation(s) not present in the first or second organic compounds,e.g., from at least partial decomposition/dehydrogenation at conditionsincluding elevated temperatures, the presence of the additionalunsaturation(s) in any intermediate or final composition can bedetermined by methods well known in the art, e.g., by FTIR and/ornuclear magnetic resonance (¹³C NMR) techniques. This catalyst precursorcomposition can be a bulk metal catalyst precursor composition or aheterogeneous (supported) metal catalyst precursor composition.

More broadly, this aspect of the present invention relates to a catalystprecursor composition comprising at least one metal from Group 6 of thePeriodic Table of the Elements, at least one metal from Groups 8-10 ofthe Periodic Table of the Elements, and a decomposition/dehydrogenationreaction product formed from at least partial decomposition of (i) afirst organic compound containing at least one first functional group or(ii) a second organic compound separate from said first organic compoundand containing at least one second functional group, but not both (i)and (ii), which decomposition/dehydrogenation reaction causes anadditional unsaturation to form in situ in the reaction product.

As used herein, the term “bulk”, when describing a mixed metal oxidecatalyst composition, indicates that the catalyst composition isself-supporting in that it does not require a carrier or support. It iswell understood that bulk catalysts may have some minor amount ofcarrier or support material in their compositions (e.g., about 20 wt %or less, about 15 wt % or less, about 10 wt % or less, about 5 wt % orless, or substantially no carrier or support, based on the total weightof the catalyst composition); for instance, bulk hydroprocessingcatalysts may contain a minor amount of a binder, e.g., to improve thephysical and/or thermal properties of the catalyst. In contrast,heterogeneous or supported catalyst systems typically comprise a carrieror support onto which one or more catalytically active materials aredeposited, often using an impregnation or coating technique.Nevertheless, heterogeneous catalyst systems without a carrier orsupport (or with a minor amount of carrier or support) are generallyreferred to as bulk catalysts and are frequently formed byco-precipitation techniques.

When the catalyst precursor is a bulk mixed metal catalyst precursorcomposition, the reaction product can be obtained by heating thecomposition (though specifically the first or second organic compounds,or the amine-containing or carboxylic acid-containing compound) to atemperature from about 195° C. to about 250° C. for a time sufficient toeffectuate a dehydrogenation, and/or an at least partial decomposition,of the first or second organic compound to form an additionalunsaturation in the reaction product in situ. Accordingly, a bulk mixedmetal hydroprocessing catalyst composition can be produced from thisbulk mixed metal catalyst precursor composition by sulfiding it undersufficient sulfiding conditions, which sulfiding should begin in thepresence of the in situ additionally unsaturated reaction product (whichmay result from at least partial decomposition, e.g., via oxidativedehydrogenation in the presence of oxygen and/or via non-oxidativedehydrogenation in the absence of an appropriate concentration ofoxygen, of typically-unfunctionalized organic portions of the first orsecond organic compounds, e.g., of an aliphatic portion of an organiccompound and/or through conjugation/aromatization of unsaturationsexpanding upon an unsaturated portion of an organic compound).

Catalyst precursor compositions and hydroprocessing catalystcompositions useful in various aspects of the present invention canadvantageously comprise (or can have metal components that consistessentially of) at least one metal from Group 6 of the Periodic Table ofElements and at least one metal from Groups 8-10 of the Periodic Tableof Elements, and optionally at least one metal from Group 5 of thePeriodic Table of Elements. Generally, these metals are present in theirsubstantially fully oxidized form, which can typically take the form ofsimple metal oxides, but which may be present in a variety of otheroxide forms, e.g., such as hydroxides, oxyhydroxides, oxycarbonates,carbonates, oxynitrates, oxysulfates, or the like, or some combinationthereof. In one preferred embodiment, the Group 6 metal(s) can be Moand/or W, and the Group 8-10 metal(s) can be Co and/or Ni. Generally,the atomic ratio of the Group 6 metal(s) to the metal(s) of Groups 8-10can be from about 2:1 to about 1:3, for example from about 5:4 to about1:2, from about 5:4 to about 2:3, from about 5:4 to about 3:4, fromabout 10:9 to about 1:2, from about 10:9 to about 2:3, from about 10:9to about 3:4, from about 20:19 to about 2:3, or from about 20:19 toabout 3:4. When the composition further comprises at least one metalfrom Group 5, that at least one metal can be V and/or Nb. When present,the amount of Group 5 metal(s) can be such that the atomic ratio of theGroup 6 metal(s) to the Group 5 metal(s) can be from about 99:1 to about1:1, for example from about 99:1 to about 5:1, from about 99:1 to about10:1, or from about 99:1 to about 20:1. Additionally or alternately,when Group 5 metal(s) is(are) present, the atomic ratio of the sum ofthe Group 5 metal(s) plus the Group (6) metal(s) compared to themetal(s) of Groups 8-10 can be from about 2:1 to about 1:3, for examplefrom about 5:4 to about 1:2, from about 5:4 to about 2:3, from about 5:4to about 3:4, from about 10:9 to about 1:2, from about 10:9 to about2:3, from about 10:9 to about 3:4, from about 20:19 to about 2:3, orfrom about 20:19 to about 3:4.

As used herein, the numbering scheme for the Periodic Table Groups is asdisclosed in Chemical and Engineering News, 63(5), 27 (1985).

The metals in the catalyst precursor compositions and in thehydroprocessing catalyst compositions according to the invention can bepresent in any suitable form prior to sulfiding, but can often beprovided as metal oxides. When provided as bulk mixed metal oxides, suchbulk oxide components of the catalyst precursor compositions and of thehydroprocessing catalyst compositions according to the invention can beprepared by any suitable method known in the art, but can generally beproduced by forming a slurry, typically an aqueous slurry, comprising(1) (a) an oxyanion of the Group 6 metal(s), such as a tungstate and/ora molybdate, or (b) an insoluble (oxide, acid) form of the Group 6metal(s), such as tungstic acid and/or molybdenum trioxide, (2) a saltof the Group 8-10 metal(s), such as nickel carbonate, and optionally,when present, (3) (a) a salt or oxyanion of a Group 5 metal, such as avanadate and/or a niobate, or (b) insoluble (oxide, acid) form of aGroup 5 metal, such as niobic acid and/or diniobium pentoxide. Theslurry can be heated to a suitable temperature, such as from about 60°C. to about 150° C., at a suitable pressure, e.g., at atmospheric orautogenous pressure, for an appropriate time, e.g., about 4 hours toabout 24 hours.

Non-limiting examples of suitable mixed metal oxide compositions caninclude, but are not limited to, nickel-tungsten oxides, cobalt-tungstenoxides, nickel-molybdenum oxides, cobalt-molybdenum oxides,nickel-molybdenum-tungsten oxides, cobalt-molybdenum-tungsten oxides,cobalt-nickel-tungsten oxides, cobalt-nickel-molybdenum oxides,cobalt-nickel-tungsten-molybdenum oxides, nickel-tungsten-niobiumoxides, nickel-tungsten-vanadium oxides, cobalt-tungsten-vanadiumoxides, cobalt-tungsten-niobium oxides, nickel-molybdenum-niobiumoxides, nickel-molybdenum-vanadium oxides,nickel-molybdenum-tungsten-niobium oxides,nickel-molybdenum-tungsten-vanadium oxides, and the like, andcombinations thereof.

Suitable mixed metal oxide compositions can advantageously exhibit aspecific surface area (as measured via the nitrogen BET method using aQuantachrome Autosorb™ apparatus) of at least about 20 m²/g, for exampleat least about 30 m²/g, at least about 40 m²/g, at least about 50 m²/g,at least about 60 m²/g, at least about 70 m²/g, or at least about 80m²/g. Additionally or alternately, the mixed metal oxide compositionscan exhibit a specific surface area of not more than about 500 m²/g, forexample not more than about 400 m²/g, not more than about 300 m²/g, notmore than about 250 m²/g, not more than about 200 m²/g, not more thanabout 175 m²/g, not more than about 150 m²/g, not more than about 125m²/g, or not more than about 100 m²/g.

After separating and drying the mixed metal oxide (slurry) composition,it can be treated, generally by impregnation, with (i) an effectiveamount of a first organic compound containing at least one amine groupor (ii) an effective amount of a second organic compound separate fromthe first organic compound and containing at least one carboxylic acidgroup, but not both (i) and (ii).

In an embodiment of any of the compositions and/or processes describedherein, the first organic compound can comprise at least 10 carbonatoms, for example can comprise from 10 to 20 carbon atoms or cancomprise a primary monoamine having from 10 to 30 carbon atoms.Additionally or alternately, the second organic compound can comprise atleast 10 carbon atoms, for example can comprise from 10 to 20 carbonatoms or can comprise only one carboxylic acid group and can have from10 to 30 carbon atoms.

Representative examples of organic compounds containing amine groups caninclude, but are not limited to, primary and/or secondary, linear,branched, and/or cyclic amines, such as triacontanylamine,octacosanylamine, hexacosanylamine, tetracosanylamine, docosanylamine,erucylamine, eicosanylamine, octadecylamine, oleylamine, linoleylamine,hexadecylamine, sapienylamine, palmitoleylamine, tetradecylamine,myristoleylamine, dodecylamine, decylamine, nonylamine, cyclooctylamine,octylamine, cycloheptylamine, heptylamine, cyclohexylamine,n-hexylamine, isopentylamine, n-pentylamine, t-butylamine, n-butylamine,isopropylamine, n-propylamine, adamantanamine, adamantanemethylamine,pyrrolidine, piperidine, piperazine, imidazole, pyrazole, pyrrole,pyrrolidine, pyrroline, indazole, indole, carbazole, norbornylamine,aniline, pyridylamine, benzylamine, aminotoluene, alanine, arginine,aspartic acid, glutamic acid, glutamine, glycine, histidine, isoleucine,leucine, lysine, phenylalanine, serine, threonine, valine,1-amino-2-propanol, 2-amino-1-propanol, diaminoeicosane,diaminooctadecane, diaminohexadecane, diaminotetradecane,diaminododecane, diaminodecane, 1,2-diaminocyclohexane,1,3-diaminocyclohexane, 1,4-diaminocyclohexane, ethylenediamine,ethanolamine, p-phenylenediamine, o-phenylenediamine,m-phenylenediamine, 1,2-propylenediamine, 1,3-propylenediamine,1,4-diaminobutane, 1,3diamino-2-propanol, and the like, and combinationsthereof. In an embodiment, the molar ratio of the Group 6 metal(s) inthe composition to the first organic compound during treatment can befrom about 1:1 to about 20:1.

The amine functional group from the first organic compound can includeprimary or secondary amines, as mentioned above, but generally does notinclude quaternary amines, and in some instances does not includetertiary amines either. Furthermore, the first organic compound canoptionally contain other functional groups besides amines. For instance,the first organic compound can comprise an aminoacid, which possesses anamine functional group and a carboxylic acid functional groupsimultaneously. Aside from carboxylic acids, other examples of suchsecondary functional groups in amine-containing organic compounds cangenerally include, but are not limited to, hydroxyls, aldehydes,anhydrides, ethers, esters, imines, imides, ketones, thiols(mercaptans), thioesters, and the like, and combinations thereof.

Additionally or alternately, the amine portion of the first organiccompound can be a part of a larger functional group in that compound, solong as the amine portion (notably the amine nitrogen and theconstituents attached thereto) retains its operability as a Lewis base.For instance, the first organic compound can comprise a urea, whichfunctional group comprises an amine portion attached to the carbonylportion of an amide group. In such an instance, the urea can beconsidered functionally as an “amine-containing” functional group forthe purposes of the present invention herein, except in situations wheresuch inclusion is specifically contradicted. Aside from ureas, otherexamples of such amine-containing functional groups that may be suitablefor satisfying the at least one amine group in the first organiccompound can generally include, but are not limited to, hydrazides,sulfonamides, and the like, and combinations thereof.

Representative examples of organic compounds containing carboxylic acidscan include, but are not limited to, primary and/or secondary, linear,branched, and/or cyclic amines, such as triacontanoic acid, octacosanoicacid, hexacosanoic acid, tetracosanoic acid, docosanoic acid, erucicacid, docosahexanoic acid, eicosanoic acid, eicosapentanoic acid,arachidonic acid, octadecanoic acid, oleic acid, elaidic acid,stearidonic acid, linoleic acid, alpha-linolenic acid, hexadecanoicacid, sapienic acid, palmitoleic acid, tetradecanoic acid, myristoleicacid, dodecanoic acid, decanoic acid, nonanoic acid, cyclooctanoic acid,octanoic acid, cycloheptanoic acid, heptanoic acid, cyclohexanoic acid,hexanoic acid, adamantanecarboxylic acid, norbornaneacetic acid, benzoicacid, salicylic acid, acetylsalicylic acid, citric acid, maleic acid,malonic acid, glutaric acid, lactic acid, oxalic acid, tartaric acid,cinnamic acid, vanillic acid, succinic acid, adipic acid, phthalic acid,isophthalic acid, terephthalic acid, ethylenediaminetetracarboxylicacids (such as EDTA), fumaric acid, alanine, arginine, aspartic acid,glutamic acid, glutamine, glycine, histidine, isoleucine, leucine,lysine, phenylalanine, serine, threonine, valine,1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, and the like, and combinationsthereof. In an embodiment, the molar ratio of the Group 6 metal(s) inthe composition to the second organic compound during treatment can befrom about 3:1 to about 20:1.

The second organic compound can optionally contain other functionalgroups besides carboxylic acids. For instance, the second organiccompound can comprise an aminoacid, which possesses a carboxylic acidfunctional group and an amine functional group simultaneously. Asidefrom amines, other examples of such secondary functional groups incarboxylic acid-containing organic compounds can generally include, butare not limited to, hydroxyls, aldehydes, anhydrides, ethers, esters,imines, imides, ketones, thiols (mercaptans), thioesters, and the like,and combinations thereof. In some embodiments, the second organiccompound can contain no additional amine or alcohol functional groups inaddition to the carboxylic acid functional group(s).

Additionally or alternately, the reactive portion of the second organiccompound can be a part of a larger functional group in that compoundand/or can be a derivative of a carboxylic acid that behaves similarlyenough to a carboxylic acid, such that the reactive portion and/orderivative retains its operability as a Lewis acid. One example of acarboxylic acid derivative can include an alkyl carboxylate ester, wherethe alkyl group does not substantially hinder (over a reasonable timescale) the Lewis acid functionality of the carboxylate portion of thefunctional group.

In certain embodiments, the organic compound(s)/additive(s) and/or thereaction product(s) are not located/incorporated within the crystallattice of the mixed metal oxide precursor composition, e.g., insteadbeing located on the surface and/or within the pore volume of theprecursor composition and/or being associated with (bound to) one ormore metals or oxides of metals in a manner that does not significantlyaffect the crystalline lattice of the mixed metal oxide precursorcomposition, as observed through XRD and/or other crystallographicspectra. It is noted that, in these certain embodiments, a sulfidedversion of the mixed metal oxide precursor composition can still haveits sulfided form affected by the organic compound(s)/additive(s) and/orthe reaction product(s), even though the oxide lattice is notsignificantly affected.

One way to attain a catalyst precursor composition containing adecomposition/dehydrogenation reaction product, such as one containingadditional unsaturations, includes: (a) treating a catalyst precursorcomposition, which comprises at least one metal from Group 6 of thePeriodic Table of the Elements and at least one metal from Groups 8-10of the Periodic Table of the Elements, with a first organic compoundcontaining at least one amine group or a second organic compoundseparate from said first organic compound and containing at least onecarboxylic acid group, but not both, to form an organically treatedprecursor catalyst composition; and (b) heating the organically treatedprecursor catalyst composition at a temperature sufficient and for atime sufficient for the first or second organic compounds to react toform an in situ product containing additional unsaturation (for example,depending upon the nature of the first or second organic compound, thetemperature can be from about 195° C. to about 250° C., such as fromabout 200° C. to about 230° C.), thereby forming theadditionally-unsaturated catalyst precursor composition.

In certain advantageous embodiments, the heating step (b) above can beconducted for a sufficiently long time so as to form additionalunsaturation(s), which may result from at least partial decomposition(e.g., oxidative and/or non-oxidative dehydrogenation and/oraromatization) of some (typically-unfunctionalized organic) portions ofthe first or second organic compounds, but generally not for so longthat the at least partial decomposition volatilizes more than 50% byweight of the first or second organic compounds. Without being bound bytheory, it is believed that additional unsaturation(s) formed in situand present at the point of sulfiding the catalyst precursor compositionto form a sulfided (hydroprocessing) catalyst composition can somehowassist in controlling one or more of the following: the size of sulfidedcrystallites; the coordination of one or more of the metals duringsulfidation, such that a higher proportion of the one or more types ofmetals are in appropriate sites for promoting desired hydroprocessingreactions (such as hydrotreating, hydrodenitrogenation,hydrodesulfurization, hydrodeoxygenation, hydrodemetallation,hydrocracking including selective hydrocracking, hydroisomerization,hydrodewaxing, and the like, and combinations thereof, and/or forreducing/minimizing undesired hydroprocessing reactions, such asaromatic saturation, hydrogenation of double bonds, and the like, andcombinations thereof) than for sulfided catalysts made in the absence ofthe in situ formed reaction product having additional unsaturation(s);and coordination/catalysis involving one or more of the metals aftersulfidation, such that a higher proportion (or each) of the one or moretypes of metals are more efficient at promoting desired hydroprocessingreactions (e.g., because the higher proportion of metal sites cancatalyze more hydrodesulfurization reactions of the same type in a giventimescale and/or because the higher proportion of the metal sites cancatalyze more difficult hydrodesulfurization reactions in a similartimescale) than for sulfided catalysts made in the absence of the insitu formed reaction product having additional unsaturation(s).

When used to make a bulk mixed metal catalyst precursor composition, thein situ reacted catalyst precursor composition can, in one embodiment,consist essentially of the reaction product, an oxide form of the atleast one metal from Group 6, an oxide form of the at least one metalfrom Groups 8-10, and optionally about 20 wt % or less of a binder(e.g., about 10 wt % or less).

After treatment of the catalyst precursor containing the at least oneGroup 6 metal and the at least one Group 8-10 metal with the first orsecond organic compounds, the organically treated catalyst precursorcomposition can be heated to a temperature high enough to form thereaction product and optionally but preferably high enough to enable anydehydrogenation/decomposition byproduct to be easily removed (e.g., inorder to drive the reaction equilibrium to the at least partiallydehydrogenated/decomposed product). Additionally or alternately, theorganically treated catalyst precursor composition can be heated to atemperature low enough so as to substantially retain the reactionproduct (containing the additional unsaturations), so as not tosignificantly decompose the reaction product, and/or so as not tosignificantly volatilize (more than 50% by weight of) the first orsecond organic compounds (whether reacted or not).

It is contemplated that the specific lower and upper temperature limitsbased on the above considerations can be highly dependent upon a varietyof factors that can include, but are not limited to, the atmosphereunder which the heating is conducted, the chemical and/or physicalproperties of the first organic compound, the second organic compound,the reaction product, and/or any reaction byproduct, or a combinationthereof. In one embodiment, the heating temperature can be at leastabout 120° C., for example at least about 150° C., at least about 165°C., at least about 175° C., at least about 185° C., at least about 195°C., at least about 200° C., at least about 210° C., at least about 220°C., at least about 230° C., at least about 240° C., or at least about250° C. Additionally or alternately, the heating temperature can be notgreater than about 400° C., for example not greater than about 375° C.,not greater than about 350° C., not greater than about 325° C., notgreater than about 300° C., not greater than about 275° C., not greaterthan about 250° C., not greater than about 240° C., not greater thanabout 230° C., not greater than about 220° C., not greater than about210° C., or not greater than about 200° C.

In one embodiment, the heating can be conducted in a low- ornon-oxidizing atmosphere (and conveniently in an inert atmosphere, suchas nitrogen). In an alternate embodiment, the heating can be conductedin a moderately- or highly-oxidizing environment. In another alternateembodiment, the heating can include a multi-step process in which one ormore heating steps can be conducted in the low- or non-oxidizingatmosphere, in which one or more heating steps can be conducted in themoderately- or highly-oxidizing environment, or both. Of course, theperiod of time for the heating in the environment can be tailored to thefirst or second organic compound, but can typically extend from about 5minutes to about 168 hours, for example from about 10 minutes to about96 hours, from about 10 minutes to about 48 hours, from about 10 minutesto about 24 hours, from about 10 minutes to about 18 hours, from about10 minutes to about 12 hours, from about 10 minutes to about 8 hours,from about 10 minutes to about 6 hours, from about 10 minutes to about 4hours, from about 20 minutes to about 96 hours, from about 20 minutes toabout 48 hours, from about 20 minutes to about 24 hours, from about 20minutes to about 18 hours, from about 20 minutes to about 12 hours, fromabout 20 minutes to about 8 hours, from about 20 minutes to about 6hours, from about 20 minutes to about 4 hours, from about 30 minutes toabout 96 hours, from about 30 minutes to about 48 hours, from about 30minutes to about 24 hours, from about 30 minutes to about 18 hours, fromabout 30 minutes to about 12 hours, from about 30 minutes to about 8hours, from about 30 minutes to about 6 hours, from about 30 minutes toabout 4 hours, from about 45 minutes to about 96 hours, from about 45minutes to about 48 hours, from about 45 minutes to about 24 hours, fromabout 45 minutes to about 18 hours, from about 45 minutes to about 12hours, from about 45 minutes to about 8 hours, from about 45 minutes toabout 6 hours, from about 45 minutes to about 4 hours, from about 1 hourto about 96 hours, from about 1 hour to about 48 hours, from about 1hour to about 24 hours, from about 1 hour to about 18 hours, from about1 hour to about 12 hours, from about 1 hour to about 8 hours, from 1hour minutes to about 6 hours, or from about 1 hour to about 4 hours.

In an embodiment, the organically treated catalyst precursor compositionand/or the catalyst precursor composition containing the reactionproduct can contain from about 4 wt % to about 20 wt %, for example fromabout 5 wt % to about 15 wt %, carbon resulting from the first andsecond organic compounds and/or from the condensation product, asapplicable, based on the total weight of the relevant composition.

Additionally or alternately, as a result of the heating step, thereaction product from the organically treated catalyst precursor canexhibit a content of unsaturated carbon atoms (which includes aromaticcarbon atoms), as measured according to peak area comparisons using ¹³CNMR techniques, of at least 29%, for example at least about 30%, atleast about 31%, at least about 32%, or at least about 33%. Furtheradditionally or alternately, the reaction product from the organicallytreated catalyst precursor can optionally exhibit a content ofunsaturated carbon atoms (which includes aromatic carbon atoms), asmeasured according to peak area comparisons using ¹³C NMR techniques, ofup to about 70%, for example up to about 65%, up to about 60%, up toabout 55%, up to about 50%, up to about 45%, up to about 40%, or up toabout 35%. Still further additionally or alternately, as a result of theheating step, the reaction product from the organically treated catalystprecursor can exhibit an increase in content of unsaturated carbon atoms(which includes aromatic carbon atoms), as measured according to peakarea comparisons using ¹³C NMR techniques, of at least about 17%, forexample at least about 18%, at least about 19%, at least about 20%, orat least about 21% (e.g., in an embodiment where the first organiccompound is oleylamine and the second organic compound is oleic acid,such that the combined unsaturation level of the unreacted compounds isabout 11.1% of carbon atoms, a ˜17% increase in unsaturated carbons uponheating corresponds to about 28.1% content of unsaturated carbon atomsin the reaction product). Yet further additionally or alternately, thereaction product from the organically treated catalyst precursor canoptionally exhibit an increase in content of unsaturated carbon atoms(which includes aromatic carbon atoms), as measured according to peakarea comparisons using ¹³C NMR techniques, of up to about 60%, forexample up to about 55%, up to about 50%, up to about 45%, up to about40%, up to about 35%, up to about 30%, or up to about 25%.

Again further additionally or alternately, as a result of the heatingstep, the reaction product from the organically treated catalystprecursor can exhibit a ratio of unsaturated carbon atoms to aromaticcarbon atoms, as measured according to peak area ratios using infraredspectroscopic techniques of a deconvoluted peak centered from about 1700cm⁻¹ to about 1730 cm⁻¹ (e.g., at about 1715 cm⁻¹), compared to adeconvoluted peak centered from about 1380 cm⁻¹ to about 1450 cm⁻¹(e.g., from about 1395 cm⁻¹ to about 1415 cm⁻¹), of at least 0.9, forexample at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least1.4, at least 1.5, at least 1.7, at least 2.0, at least 2.2, at least2.5, at least 2.7, or at least 3.0. Again still further additionally oralternately, the reaction product from the organically treated catalystprecursor can exhibit a ratio of unsaturated carbon atoms to aromaticcarbon atoms, as measured according to peak area ratios using infraredspectroscopic techniques of a deconvoluted peak centered from about 1700cm⁻¹ to about 1730 cm⁻¹ (e.g., at about 1715 cm⁻¹), compared to adeconvoluted peak centered from about 1380 cm⁻¹ to about 1450 cm⁻¹(e.g., from about 1395 cm⁻¹ to about 1415 cm⁻¹), of up to 15, forexample up to 10, up to 8.0, up to 7.0, up to 6.0, up to 5.0, up to 4.5,up to 4.0, up to 3.5, or up to 3.0.

A (sulfided) hydroprocessing catalyst composition can then be producedby sulfiding the catalyst precursor composition containing the reactionproduct. Sulfiding is generally carried out by contacting the catalystprecursor composition containing the reaction product with asulfur-containing compound (e.g., elemental sulfur, hydrogen sulfide,polysulfides, or the like, or a combination thereof, which may originatefrom a fossil/mineral oil stream, from a biocomponent-based oil stream,from a combination thereof, or from a sulfur-containing stream separatefrom the aforementioned oil stream(s)) at a temperature and for a timesufficient to substantially sulfide the composition and/or sufficient torender the sulfided composition active as a hydroprocessing catalyst.For instance, the sulfidation can be carried out at a temperature fromabout 300° C. to about 400° C., e.g., from about 310° C. to about 350°C., for a period of time from about 30 minutes to about 96 hours, e.g.,from about 1 hour to about 48 hours or from about 4 hours to about 24hours. The sulfiding can generally be conducted before or aftercombining the metal (oxide) containing composition with a binder, ifdesired, and before or after forming the composition into a shapedcatalyst. The sulfiding can additionally or alternately be conducted insitu in a hydroprocessing reactor. Obviously, to the extent that areaction product of the first or second organic compounds containsadditional unsaturations formed in situ, it would generally be desirablefor the sulfidation (and/or any catalyst treatment after the organictreatment) to significantly maintain the in situ formed additionalunsaturations of said reaction product.

The sulfided catalyst composition can exhibit a layered structurecomprising a plurality of stacked YS₂ layers, where Y is the Group 6metal(s), such that the average number of stacks (typically for bulkorganically treated catalysts) can be from about 1.5 to about 3.5, forexample from about 1.5 to about 3.0, from about 2.0 to about 3.3, fromabout 2.0 to about 3.0, or from about 2.1 to about 2.8. For instance,the treatment of the metal (oxide) containing precursor compositionaccording to the invention can afford a decrease in the average numberof stacks of the treated precursor of at least about 0.8, for example atleast about 1.0, at least about 1.2, at least about 1.3, at least about1.4, or at least about 1.5, as compared to an untreated metal (oxide)containing precursor composition. As such, the number of stacks can beconsiderably less than that obtained with an equivalent sulfided mixedmetal (oxide) containing precursor composition produced without thefirst or second organic compound treatment. The reduction in the averagenumber of stacks can be evidenced, e.g., via X-ray diffraction spectraof relevant sulfided compositions, in which the (002) peak appearssignificantly broader (as determined by the same width at thehalf-height of the peak) than the corresponding peak in the spectrum ofthe sulfided mixed metal (oxide) containing precursor compositionproduced without the organic treatment (and/or, in certain cases, withonly a single organic compound treatment using an organic compoundhaving less than 10 carbon atoms) according to the present invention.Additionally or alternately to X-ray diffraction, transmission electronmicroscopy (TEM) can be used to obtain micrographs of relevant sulfidedcompositions, including multiple microcrystals, within which micrographimages the multiple microcrystals can be visually analyzed for thenumber of stacks in each, which can then be averaged over the micrographvisual field to obtain an average number of stacks that can evidence areduction in average number of stacks compared to a sulfided mixed metal(oxide) containing precursor composition produced without the organictreatment (and/or, in certain cases, with only a single organic compoundtreatment) according to the present invention.

The sulfided catalyst composition described above can be used as ahydroprocessing catalyst, either alone or in combination with a binder.If the sulfided catalyst composition is a bulk catalyst, then only arelatively small amount of binder may be added. However, if the sulfidedcatalyst composition is a heterogeneous/supported catalyst, then usuallythe binder is a significant portion of the catalyst composition, e.g.,at least about 40 wt %, at least about 50 wt %, at least about 60 wt %,or at least about 70 wt %; additionally or alternately forheterogeneous/supported catalysts, the binder can comprise up to about95 wt % of the catalyst composition, e.g., up to about 90 wt %, up toabout 85 wt %, up to about 80 wt %, up to about 75 wt %, or up to about70 wt %. Non-limiting examples of suitable binder materials can include,but are not limited to, silica, silica-alumina (e.g., conventionalsilica-alumina, silica-coated alumina, alumina-coated silica, or thelike, or a combination thereof), alumina (e.g., boehmite,pseudo-boehmite, gibbsite, or the like, or a combination thereof),titania, zirconia, cationic clays or anionic clays (e.g., saponite,bentonite, kaoline, sepiolite, hydrotalcite, or the like, or acombination thereof), and mixtures thereof. In some preferredembodiments, the binder can include silica, silica-alumina, alumina,titania, zirconia, and mixtures thereof. These binders may be applied assuch or after peptization. It may also be possible to apply precursorsof these binders that, during precursor synthesis, can be converted intoany of the above-described binders. Suitable precursors can include,e.g., alkali metal aluminates (alumina binder), water glass (silicabinder), a mixture of alkali metal aluminates and water glass(silica-alumina binder), a mixture of sources of a di-, tri-, and/ortetravalent metal, such as a mixture of water-soluble salts ofmagnesium, aluminum, and/or silicon (cationic clay and/or anionic clay),chlorohydrol, aluminum sulfate, or mixtures thereof.

Generally, the binder material to be used can have lower catalyticactivity than the remainder of the catalyst composition, or can havesubstantially no catalytic activity at all (less than about 5%, based onthe catalytic activity of the bulk catalyst composition being about100%). Consequently, by using a binder material, the activity of thecatalyst composition may be reduced. Therefore, the amount of bindermaterial to be used, at least in bulk catalysts, can generally depend onthe desired activity of the final catalyst composition. Binder amountsup to about 25 wt % of the total composition can be suitable (whenpresent, from above 0 wt % to about 25 wt %), depending on the envisagedcatalytic application. However, to take advantage of the resultingunusual high activity of bulk catalyst compositions according to theinvention, binder amounts, when added, can generally be from about 0.5wt % to about 20 wt % of the total catalyst composition.

If desired in bulk catalyst cases, the binder material can be compositedwith a source of a Group 6 metal and/or a source of a non-noble Group8-10 metal, prior to being composited with the bulk catalyst compositionand/or prior to being added during the preparation thereof. Compositingthe binder material with any of these metals may be carried out by anyknown means, e.g., impregnation of the (solid) binder material withthese metal(s) sources.

A cracking component may also be added during catalyst preparation. Whenused, the cracking component can represent from about 0.5 wt % to about30 wt %, based on the total weight of the catalyst composition. Thecracking component may serve, for example, as an isomerization enhancer.Conventional cracking components can be used, e.g., a cationic clay, ananionic clay, a zeolite (such as ZSM-5, zeolite Y, ultra-stable zeoliteY, zeolite X, an AlPO, a SAPO, or the like, or a combination thereof),amorphous cracking components (such as silica-alumina or the like), or acombination thereof. It is to be understood that some materials may actas a binder and a cracking component at the same time. For instance,silica-alumina may simultaneously have both a cracking and a bindingfunction.

If desired, the cracking component may be composited with a Group 6metal and/or a Group 8-10 non-noble metal, prior to being compositedwith the catalyst composition and/or prior to being added during thepreparation thereof. Compositing the cracking component with any ofthese metals may be carried out by any known means, e.g., impregnationof the cracking component with these metal(s) sources. When both acracking component and a binder material are used and when compositingof additional metal components is desired on both, the compositing maybe done on each component separately or may be accomplished by combiningthe components and doing a single compositing step.

The selection of particular cracking components, if any, can depend onthe intended catalytic application of the final catalyst composition.For instance, a zeolite can be added if the resulting composition is tobe applied in hydrocracking or fluid catalytic cracking. Other crackingcomponents, such as silica-alumina or cationic clays, can be added ifthe final catalyst composition is to be used in hydrotreatingapplications. The amount of added cracking material can depend on thedesired activity of the final composition and the intended application,and thus, when present, may vary from above 0 wt % to about 80 wt %,based on the total weight of the catalyst composition. In a preferredembodiment, the combination of cracking component and binder materialcan comprise less than 50 wt % of the catalyst composition, for example,less than about 40 wt %, less than about 30 wt %, less than about 20 wt%, less than about 15 wt %, or less than about 10 wt %.

If desired, further materials can be added, in addition to the metalcomponents already added, such as any material that would be addedduring conventional hydroprocessing catalyst preparation. Suitableexamples of such further materials can include, but are not limited to,phosphorus compounds, boron compounds, fluorine-containing compounds,sources of additional transition metals, sources of rare earth metals,fillers, or mixtures thereof.

The mixed metal oxide catalyst compositions described herein can be usedubiquitously in many hydroprocessing processes to treat any of aplurality of feeds under wide-ranging reaction conditions, such astemperatures from about 200° C. to about 450° C., hydrogen pressuresfrom about 5 barg to about 300 barg (about 0.5 MPag to about 30 MPag),LHSVs from about 0.05 hr⁻¹ to about 10 hr⁻¹, and hydrogen treat gasrates from about 200 scf/bbl to about 10,000 scf/bbl (about 34 Nm³/m³ toabout 1700 Nm³/m³). The term “hydroprocessing,” as used herein, shouldbe understood to encompass all processes in which a hydrocarbon feed isreacted with hydrogen (e.g., at the temperatures and pressures notedabove), and specifically includes hydrodemetallation, hydrodewaxing,hydrotreating, hydrogenation, hydrodesulfurization,hydrodenitrogenation, hydrodearomatization, hydroisomerization, andhydrocracking (including selective hydrocracking), as well ascombinations thereof. Depending on the type of hydroprocessing and thereaction conditions, the products of hydroprocessing may show improvedviscosities, viscosity indices, saturate contents, low temperatureproperties, volatilities, depolarization, or the like, or combinationsthereof. It should be understood that hydroprocessing can be practicedin one or more reaction zones, in either countercurrent flow orco-current flow mode. By countercurrent flow mode is meant a processmode in which the feedstream flows in a direction opposite to the flowof hydrogen-containing treat gas. The hydroprocessing reactor can alsobe operated in any suitable catalyst-bed arrangement mode (e.g., fixedbed, slurry bed, ebullating bed, or the like).

A wide range of hydrocarbon feedstocks can be hydroprocessed inaccordance with the present invention. Suitable feedstocks can include,but are not limited to, whole and reduced petroleum crudes, atmosphericand vacuum residua, propane deasphalted residua (e.g., brightstock),cycle oils, FCC tower bottoms, gas oils (including atmospheric andvacuum gas oils, as well as coker gas oils), light to heavy distillates(including raw virgin distillates), hydrocrackates, hydrotreated oils,dewaxed oils, slack waxes, Fischer-Tropsch waxes, raffinates, naphthas,and the like, and combinations thereof. In particular, due to theincreased activity of the catalysts made according to the invention, aparticularly large advantage can be seen for hydrocarbon feedstocks thatare more difficult to process, e.g., because of increased sulfur and/ornitrogen content and/or because of an increased content of particularlydifficult sulfur and/or nitrogen content, which can typically include,but is not limited to, heavier and more disadvantaged feeds, such asgasoils, heavy distillates (including diesel), cycle oils, FCC towerbottoms, waxes, residua, certain whole or heavier reduced petroleumcrudes, and the like, and combinations thereof.

Additionally or alternately, the hydrocarbon feedstock can includerenewable or biofeed in the form of lipid material, so long as there issufficient sulfur content in the feedstock to implicate the use ofhydroprocessing catalysts such as those described herein. The term“lipid material,” as used herein, is a composition comprised ofbiological materials. Generally, these biological materials includevegetable fats/oils, animal fats/oils, fish oils, pyrolysis oils, andalgae lipids/oils, as well as components of such materials. Morespecifically, the lipid material includes one or more type of lipidcompounds. Lipid compounds are typically biological compounds that areinsoluble in water, but soluble in nonpolar (or fat) solvents.Non-limiting examples of such solvents include alcohols, ethers,chloroform, alkyl acetates, benzene, and combinations thereof.

Major classes of lipids include, but are not necessarily limited to,fatty acids, glycerol-derived lipids (including fats, oils andphospholipids), sphingosine-derived lipids (including ceramides,cerebrosides, gangliosides, and sphingomyelins), steroids and theirderivatives, terpenes and their derivatives, fat-soluble vitamins,certain aromatic compounds, and long-chain alcohols and waxes.

In living organisms, lipids generally serve as the basis for cellmembranes and as a form of fuel storage. Lipids can also be foundconjugated with proteins or carbohydrates, such as in the form oflipoproteins and lipopolysaccharides.

Examples of vegetable oils that can be used include, but are not limitedto, rapeseed (canola) oil, soybean oil, coconut oil, sunflower oil, palmoil, palm kernel oil, peanut oil, linseed oil, tall oil, corn oil,castor oil, jatropha oil, jojoba oil, olive oil, flaxseed oil, camelinaoil, safflower oil, babassu oil, tallow oil, and rice bran oil.

Vegetable oils as referred to herein can also include processedvegetable oil material. Non-limiting examples of processed vegetable oilmaterial include fatty acids and fatty acid alkyl esters. Alkyl esterstypically include C₁-C₅ alkyl esters. One or more of methyl, ethyl, andpropyl esters are preferred.

Examples of animal fats that can be used include, but are not limitedto, beef fat (tallow), hog fat (lard), turkey fat, fish fat/oil, andchicken fat. The animal fats can be obtained from any suitable sourceincluding restaurants and meat production facilities.

Animal fats as referred to herein also include processed animal fatmaterial. Non-limiting examples of processed animal fat material includefatty acids and fatty acid alkyl esters. Alkyl esters typically includeC₁-C₅ alkyl esters. One or more of methyl, ethyl, and propyl esters arepreferred.

Algae oils or lipids are typically contained in algae in the form ofmembrane components, storage products, and metabolites. Certain algalstrains, particularly microalgae such as diatoms and cyanobacteria,contain proportionally high levels of lipids. Algal sources for thealgae oils can contain varying amounts, e.g., from about 2 wt % to about40 wt % of lipids, based on total weight of the biomass itself.

Algal sources for algae oils include, but are not limited to,unicellular and multicellular algae. Examples of such algae include arhodophyte, chlorophyte, heterokontophyte, tribophyte, glaucophyte,chlorarachniophyte, euglenoid, haptophyte, cryptomonad, dinoflagellum,phytoplankton, and the like, and combinations thereof. In oneembodiment, algae can be of the classes Chlorophyceae and/or Haptophyta.Specific species can include, but are not limited to, Neochlorisoleoabundans, Scenedesmus dimorphus, Euglena gracilis, Phaeodactylumtricornutum, Pleurochrysis carterae, Prymnesium parvum, Tetraselmischui, and Chlamydomonas reinhardtii.

Additionally or alternately, non-limiting examples of microalgae caninclude, for example, Achnanthes, Amphiprora, Amphora, Ankistrodesmus,Asteromonas, Boekelovia, Borodinella, Botryococcus, Bracteococcus,Chaetoceros, Carteria, Chlamydomonas, Chlorococcum, Chlorogonium,Chlorella, Chroomonas, Chrysosphaera, Cricosphaera, Crypthecodinium,Cryptomonas, Cyclotella, Dunaliella, Ellipsoidon, Emiliania,Eremosphaera, Ernodesmius, Euglena, Franceia, Fragilaria, Gloeothamnion,Haematococcus, Halocafeteria, Hymenomonas, Isochrysis, Lepocinclis,Micractinium, Monoraphidium, Nannochloris, Nannochloropsis, Navicula,Neochloris, Nephrochloris, Nephroselmis, Nitzschia, Ochromonas,Oedogonium, Oocystis, Ostreococcus, Pavlova, Parachlorella, Pascheria,Phaeodactylum, Phagus, Platymonas, Pleurochrysis, Pleurococcus,Prototheca, Pseudochlorella, Pyramimonas, Pyrobotrys, Scenedesmus,Skeletonema, Spyrogyra, Stichococcus, Tetraselmis, Thalassiosira,Viridiella, and Volvox species, including freshwater and marinemicroalgal species of these or other genera.

Further additionally or alternately, the algae used according to theinvention can be characterized as cyanobacteria. Non-limiting examplesof cyanobacteria can include, for example, Agmenellum, Anabaena,Anabaenopsis, Anacystis, Aphanizomenon, Arthrospira, Asterocapsa,Borzia, Calothrix, Chamaesiphon, Chlorogloeopsis, Chroococcidiopsis,Chroococcus, Crinalium, Cyanobacterium, Cyanobium, Cyanocystis,Cyanospira, Cyanothece, Cylindrospermopsis, Cylindrospermum,Dactylococcopsis, Dermocarpella, Fischerella, Fremyella, Geitleria,Geitlerinema, Gloeobacter, Gloeocapsa, Gloeothece, Halospirulina,Iyengariella, Leptolyngbya, Limnothrix, Lyngbya, Microcoleus,Microcystis, Myxosarcina, Nodularia, Nostoc, Nostochopsis, Oscillatoria,Phormidium, Planktothrix, Pleurocapsa, Prochlorococcus, Prochloron,Prochlorothrix, Pseudanabaena, Rivularia, Schizothrix, Scytonema,Spirulina, Stanieria, Starria, Stigonema, Symploca, Synechococcus,Synechocystis, Tolypothrix, Trichodesmium, Tychonema, and Xenococcusspecies, including freshwater and marine cyanobacterial species of theseor other genera.

One way to judge the effectiveness of the treatment with the first orsecond organic compounds on the catalyst precursor compositionsaccording to the invention can be based on relative catalytic activityfor a given reaction process (e.g., hydrodenitrogenation,hydrodesulfurization, hydrodeoxygenation, or the like). Such relativecatalytic activity can further be expressed by comparing standardcatalyst characteristics, such as weight, volume, moles of a certain(active metal) component, or the like, to normalize the results foruniversal comparison amongst catalysts useful in that given reactionprocess. Even so, such standard characteristics may not be universallycomparable—for example, because supported catalysts tend to have most oftheir catalytically active metal sites spread out over the supportsurface (and thus available for catalyzation), comparison of relativeactivities between supported catalysts and bulk catalysts may beinappropriate or uninformative, since proportionally fewer of thecatalytically active metal sites in a bulk catalyst are disposed on thesurface (and thus available for catalyzation). Nevertheless, amongstcatalysts of similar type (e.g., Group 6/Group 8-10 bulk catalysts),relative catalytic activity can be a particularly useful comparison. Inthe instant case, unless otherwise stated, relative volumetric activity(RVA), which normalizes activity herein to a unit volume based oncatalyst loading and catalyst density, and relative molar activity(RMA), which normalizes activity herein to the collective number ofmoles of non-Group 8-10 catalytically active metal(s), are based onhydrodenitrogenation (HDN) reactions, assuming ˜1.0 order kinetics. ForRMA values, the non-Group 8-10 catalytically active metal(s) includesany and all Group 6 catalytically active metal(s) (e.g., Mo and/or W),as well as other catalytically active metal(s) such as Group 5 (e.g., Nband/or V). All the RMA values herein were taken from experiments wherecatalyst was “on stream” (i.e., contacting the feed at reactionconditions such as hydroprocessing reaction conditions) for betweenabout 10 days and about 30 days, and RMA values were only reported whenthey appeared to stabilize.

As a result, one characterization of the compositions, methods of makingsuch compositions, and methods of use according to the presentinvention, additionally or alternately to one or more others describedherein, can include an increase in RMA for catalyst compositionscontaining a reaction product of first or second organic compounds (butnot both) and/or in methods containing an organic treatment using firstor second organic compounds (but not both) according to the invention ofat least 25%, compared to catalyst compositions without, or prior to, anorganic treatment using first or second organic compounds and/or methodscontaining no, or prior to any, organic treatment; for example, the RMAincrease can be at least 30%, at least 32%, at least 34%, at least 36%,at least 38%, at least 40%, at least 42%, at least 44%, at least 46%, atleast 48%, at least 50%, at least 51%, at least 52%, at least 53%, atleast 54%, or at least 55%. Additionally or alternately, the RMAincrease can be up to 200%, for example up to 150%, up to 125%, up to100%, up to 90%, up to 80%, up to 70%, up to 65%, up to 60%, up to 57%,up to 56%, up to 55%, up to 54%, up to 53%, up to 52%, up to 51%, or upto 50%, compared to catalyst compositions without, or prior to, anorganic treatment using first or second organic compounds (but not both)and/or methods containing no, or prior to any, organic treatment.Further additionally or alternately, the compositions, methods of makingsuch compositions, and methods of use according to the presentinvention, can exhibit an increase in RMA for catalyst compositionscontaining a reaction product of first or second organic compounds (butnot both) and/or in methods containing an organic treatment using firstor second organic compounds (but not both) according to the invention ofat least 20%, compared to catalyst compositions with an organictreatment using only a single organic compound having less than 10carbon atoms and/or to methods containing an organic treatment usingonly a single organic compound having less than 10 carbon atoms; forexample, the RMA increase can be at least 25%, at least 30%, at least35%, at least 40%, at least 45%, at least 46%, at least 47%, at least48%, at least 49%, at least 50%, at least 51%, at least 52%, at least53%, at least 54%, at least 55%, at least 60%, at least 65%, at least70%, at least 75%, at least 80%, or at least 85%. Still furtheradditionally or alternately, the RMA increase can be up to 200%, forexample up to 150%, up to 125%, up to 100%, up to 90%, up to 80%, up to70%, up to 65%, up to 60%, up to 57%, up to 56%, up to 55%, up to 54%,up to 53%, up to 52%, up to 51%, or up to 50%, compared to compared tocatalyst compositions with an organic treatment using only a singleorganic compound having less than 10 carbon atoms and/or to methodscontaining an organic treatment using only a single organic compoundhaving less than 10 carbon atoms.

Additionally or alternately, the present invention can include thefollowing embodiments.

Embodiment 1

A catalyst precursor composition comprising at least one metal fromGroup 6 of the Periodic Table of the Elements, at least one metal fromGroups 8-10 of the Periodic Table of the Elements, and a reactionproduct formed from (i) a first organic compound containing at least oneamine group and at least 10 carbons or (ii) a second organic compoundcontaining at least one carboxylic acid group and at least 10 carbons,but not both (i) and (ii), wherein the reaction product containsadditional unsaturated carbon atoms, relative to (i) the first organiccompound or (ii) the second organic compound, wherein the metals of thecatalyst precursor composition are arranged in a crystal lattice, andwherein the reaction product is not located within the crystal lattice.

Embodiment 2

A process for producing a catalyst precursor composition containing insitu formed unsaturated carbon atoms, the process comprising: (a)treating a catalyst precursor composition comprising at least one metalfrom Group 6 of the Periodic Table of the Elements, at least one metalfrom Groups 8-10 of the Periodic Table of the Elements, with a firstorganic compound containing at least one amine group and at least 10carbon atoms or a second organic compound containing at least onecarboxylic acid group and at least 10 carbon atoms, to form anorganically treated precursor catalyst composition; and (b) heating saidorganically treated precursor catalyst composition at a temperature fromabout 195° C. to about 250° C. for a time sufficient for the first orsecond organic compounds to react to form additional in situ unsaturatedcarbon atoms not present in the first or second organic compounds, butnot for so long that more than 50% by weight of the first or secondorganic compound is volatilized, thereby forming a catalyst precursorcomposition containing in situ formed unsaturated carbon atoms.

Embodiment 3

The catalyst precursor composition or the process of any one of theprevious embodiments, wherein said at least one metal from Group 6 isMo, W, or a combination thereof, and wherein said at least one metalfrom Groups 8-10 is Co, Ni, or a combination thereof.

Embodiment 4

The catalyst precursor composition or the process of any one of theprevious embodiments, wherein said catalyst precursor compositionfurther comprises at least one metal from Group 5 of the Periodic Tableof the Elements, for example V, Nb, or a combination thereof.

Embodiment 5

The catalyst precursor composition or the process of any one of theprevious embodiments, wherein said first organic compound comprises aprimary monoamine having from 10 to 30 carbon atoms, and/or wherein saidsecond organic compound comprises only one carboxylic acid group and hasfrom 10 to 30 carbon atoms.

Embodiment 6

A bulk mixed metal catalyst precursor composition produced by heatingthe composition of any one of embodiments 1 and 3-5 to a temperaturefrom about 195° C. to about 250° C. for a time sufficient for the firstor second organic compounds to form a reaction product in situ thatcontains unsaturated carbon atoms not present in the first or secondorganic compounds.

Embodiment 7

A bulk mixed metal hydroprocessing catalyst composition produced bysulfiding the catalyst precursor composition of embodiment 6.

Embodiment 8

The process of any one of embodiments 2-5, wherein the catalystprecursor composition containing in situ formed unsaturated carbon atomsis a bulk metal hydroprocessing catalyst precursor compositionconsisting essentially of the reaction product, an oxide form of the atleast one metal from Group 6, an oxide form of the at least one metalfrom Groups 8-10, and optionally about 20 wt % or less of a binder.

Embodiment 9

A process for producing a sulfided hydroprocessing catalyst composition,comprising sulfiding the catalyst precursor composition containing insitu formed unsaturated carbon atoms made according to the process ofany one of embodiments 2-5 and 8 under conditions sufficient to producethe sulfided hydroprocessing catalyst composition.

Embodiment 10

A catalyst precursor composition containing in situ formed unsaturatedcarbon atoms made according to the process of any one of embodiments 2-5and 8-9.

Embodiment 11

A sulfided hydroprocessing catalyst composition made according to theprocess of embodiment 10.

Embodiment 12

The catalyst precursor composition, the hydroprocessing catalyst, or theprocess of any one of the previous embodiments, wherein one or more ofthe following are satisfied: the catalyst precursor composition exhibitsa content of unsaturated carbon atoms, as measured according to peakarea comparisons using ¹³C NMR techniques, of at least 29%; the catalystprecursor composition exhibits an increase in content of unsaturatedcarbon atoms, as measured according to peak area comparisons using ¹³CNMR techniques, of at least about 17%, compared to a collective contentof unsaturated carbon atoms present in the first or second organiccompound; the catalyst precursor composition exhibits a ratio ofunsaturated carbon atoms to aromatic carbon atoms, as measured accordingto peak area ratios using infrared spectroscopic techniques of adeconvoluted peak centered from about 1700 cm⁻¹ to about 1730 cm⁻¹,compared to a deconvoluted peak centered from about 1380 cm⁻¹ to about1450 cm⁻¹, of at least 0.9; and the catalyst precursor compositionexhibits a ratio of unsaturated carbon atoms to aromatic carbon atoms,as measured according to peak area ratios using infrared spectroscopictechniques of a deconvoluted peak centered from about 1700 cm⁻¹ to about1730 cm⁻¹, compared to a deconvoluted peak centered from about 1380 cm⁻¹to about 1450 cm⁻¹, of up to 15.

Embodiment 13

A process for producing a sulfided hydroprocessing catalyst composition,comprising sulfiding the catalyst precursor composition of any one ofembodiments 1, 3-6, 10, and 12 or made according to the process of anyone of embodiments 2-5, 8-9, and 12 under conditions sufficient toproduce the sulfided hydroprocessing catalyst composition, wherein oneor more of the following are satisfied: the sulfided hydroprocessingcatalyst composition exhibits a layered structure comprising a pluralityof stacked layers of sulfided Group 6 metal(s), such that the averagenumber of stacked layers is from about 1.5 to about 3.5; the sulfidedhydroprocessing catalyst composition exhibits a layered structurecomprising a plurality of stacked layers of sulfided Group 6 metal(s),such that the average number of stacked layers is at least about 0.8stacked layers less than an identical sulfided hydroprocessing catalystcomposition that has not been treated using first or second organiccompounds; upon exposure of the sulfided hydroprocessing catalystcomposition to a vacuum gasoil feedstock under hydroprocessingconditions, the sulfided hydroprocessing catalyst composition exhibits ahydrodenitrogenation RMA of at least 57% greater than a sulfidedcatalyst composition that has not been treated using first or secondorganic compounds; upon exposure of the sulfided hydroprocessingcatalyst composition to a vacuum gasoil feedstock under hydroprocessingconditions, the sulfided hydroprocessing catalyst composition exhibits ahydrodenitrogenation RMA of up to 500% greater than a sulfided catalystcomposition that has not been treated using first or second organiccompounds; upon exposure of the sulfided hydroprocessing catalystcomposition to a vacuum gasoil feedstock under hydroprocessingconditions, the sulfided hydroprocessing catalyst composition exhibits ahydrodenitrogenation RMA at least 30% greater than a sulfided catalystcomposition that has been treated with only a single organic compoundhaving less than 10 carbon atoms; and upon exposure of the sulfidedhydroprocessing catalyst composition to a vacuum gasoil feedstock underhydroprocessing conditions, the sulfided hydroprocessing catalystcomposition exhibits a hydrodenitrogenation RMA up to 500% greater thana sulfided catalyst composition that has been treated with only a singleorganic compound having less than 10 carbon atoms.

The invention will now be more particularly described with reference tothe accompanying drawings and the following non-limiting Examples.

EXAMPLES

In the Examples, X-ray diffraction spectra were collected on a RigakuDmax diffractometer with Cu K_(α) radiation. Thermogravimetry, DynamicThermal Analysis, and Mass Spectrometry (TG/DTA/MS) data were collectedon a Mettler TGA 851 thermal balance, interfaced with a BalzersThermostar quadrupole mass spectrometer, which was equipped with asecondary electron multiplier. Weight loss during air oxidation at about800° C. was monitored both before and after the thermal treatment of theorganically treated catalyst precursor to estimate the amount of organiccomponents present in the sample. Also, the sulfided phases can beoxidized to form oxides (a weight loss event), thus allowing estimationof additional weight loss due to retention of the organic component inthe sulfide phase.

For TEM measurements, samples of the sulfided compositions were crushedinto pieces (less than about 100 nm thick), dusted onto holey-carboncoated grids, and examined in a bright field imaging mode of a PhilipsCM200F instrument. About 250-350 different crystals of each sulfidedcomposition were examined, and the numbers of stacks were counted andaveraged. Numbers of stacks reported herein are thus average values.

Sulfiding of the different catalyst precursors produced in the Exampleswas conducted by placing about 2-4 grams of the precursor in either thedried or calcined state in a quartz boat, which in turn was insertedinto a horizontal quartz tube and placed into a Lindberg furnace. Whilestill at room temperature, a flow of about 200 cm³/min of about 10%H₂S/H₂ was admitted for about 15 minutes, and then the temperature wasraised to about 400° C. in about 45 minutes with the ˜10% H₂S/H₂ stillflowing at about 200 cm³/min This flow was continued for about 2 hoursat about 400° C. The sample was then cooled in flowing ˜10% H₂S/H₂ toabout room temperature (about 20-25° C.) and held there for about 30minutes at roughly the same flow. After about 300 cm³/min of N₂ flow forabout 30 minutes, a passivation gas comprising about 1% O₂ in He wasintroduced at about 50 cm³/min at about room temperature and was leftovernight (about 12-18 hours). The sample was then removed from thefurnace.

Preparation Examples Comparative Example 1 Preparation of NiWO₄ andNiMo_(0.5)W_(0.5)O₄ (No Organics)

A metastable hexagonal variant of NiWO₄ is formed by a solid-slurryreaction between nickel carbonate and tungstic acid. About 5.93 gramsnickel carbonate and about 12.49 grams tungstic acid were added to about150 mL of water to form a suspension, which was added to a ˜275 mLWeflon™ reaction vessel. The vessel was then heated (in a microwaveoven) to about 150° C. for about 6 hours, cooled to about roomtemperature (about 20-25° C.), and filtered and dried at about 100° C.After drying, the material was heated in a box furnace in air at a ramprate of about 2° C./min up to a final temperature of about 300° C. andwas held at that temperature for about 4 hours (e.g., to calcine). Aportion of this material was labeled as catalyst A. FIG. 1 shows thex-ray diffraction spectrum of this sample, which crystallized in thehexagonal nickel tungstate phase. The Ni₁Mo_(0.5)W_(0.5)O₄ catalyst,catalyst B, was prepared in an analogous method, but half the moles oftungstic acid were replaced with MoO₃.

Example 1 Preparation of NiWO₄(1,2DACH)₂ and NiWO₄(1,2DACH)₂/(CitricAcid)

Into a ˜1000 cc glass reaction flask equipped with a reflux condenser,about 16.6 grams nickel carbonate (˜0.14 moles Ni) and about 35.0 gramstungstic acid (˜0.14 moles W) were added to about 150 mL of water, intowhich about 32.0 grams 1,2-diaminocyclohexane (1,2DACH; ˜0.28 moles,technical grade, Aldrich) had been previously dissolved. A stiffer,thermometer, and reflux condenser was attached to the flask. Thereaction mixture was continuously stirred and heated to about 90° C. andheld overnight (about 18 hours). The solid so obtained was filtered anddried at about 100° C. The weight obtained, about 39.5 g, compares witha calculated weight of about 74.9 g. The X-ray diffraction spectrum ofthe dried product is shown in FIG. 2 and was labeled as catalyst 1a.

A portion of catalyst 1a [NiWO₄(1,2DACH)₂] was treated in a flowingnitrogen stream (about 200 cm³/min) in a quartz line tube furnace, witha heating rate of about 2° C./min, to a final temperature of about 320°C. and was held at that temperature for about 90 minutes. It was thencooled to approximately room temperature and removed from the furnace.This catalyst was labeled as catalyst 1a//N₂. Another portion ofcatalyst 1a was impregnated (by incipient wetness) with citric acid suchthat the molar ratio of tungsten to citric acid was about 1:0.33. Thissample was dried at about 100° C. overnight and labeled as catalyst 1b.A portion of catalyst 1b was treated in a flowing nitrogen stream (about200 cm³/min) in a quartz line tube furnace, with a heating rate of about2° C./min, to a final temperature of about 320° C. and was held at thattemperature for about 90 minutes. It was then cooled to approximatelyroom temperature and removed from the furnace. This catalyst was labeledas catalyst 1b//N₂.

Example 2 Preparation of NiWO₄(ethylenediamine)₃

A tris-ethylenediamine complex of NiWO₄ was prepared by the reaction ofabout 5.94 grams nickel carbonate, about 12.49 grams tungstic acid, andabout 9.02 grams ethylenediamine, all placed along with about 10 mLwater into a ˜275 mL Weflon™ reaction vessel. The vessel was sealed andthe reaction mixture continuously stirred and heated at about 10° C./minto about 60° C. (in a microwave reactor) and was held at thattemperature for about 6 hours. After cooling and filtering, about 9.4grams of the known phase of the tris-ethylenediamine nickel tungstatewas identified and labeled catalyst 2. FIG. 3 shows the X-raydiffraction pattern of this phase.

Example 3 Preparation of NiWO₄/(en)₁/Citric Acid_(0.33)/N₂

The NiWO₄ precursor produced in Comparative Example 1 was impregnatedwith ethylenediamine (en), such that the mole ratio of tungsten to enwas about 1:1. A portion of this sample was labeled catalyst 3a. Anotherportion of catalyst 3a was treated in a flowing nitrogen stream (about200 cm³/min) in a quartz line tube furnace, with a heating rate of about2° C./min, to a final temperature of about 320° C. and was held at thattemperature for about 90 minutes. It was then cooled to approximatelyroom temperature and removed from the furnace. This catalyst was labeledas catalyst 3a//N₂.

The portion of the catalyst 3a that had been impregnated with en anddried at about 100° C. was then further impregnated (to the incipientwetness point) with citric acid dissolved in water, such that the molarratio of en to citric acid was about 1:0.33. This sample was then driedagain at about 100° C. and labeled as catalyst 3b. A portion of thiscatalyst 3b sample was treated in a flowing nitrogen stream (about 200cm³/min) in a quartz-lined tube furnace, with a heating rate of about 2°C./min, to a final temperature of about 320° C. and was held at thattemperature for about 90 minutes. It was then cooled to approximatelyroom temperature and removed from the furnace. It was labeled ascatalyst 3b//N₂.

A separate portion of the NiWO₄ was impregnated with only citric acid,such that the molar ratio of tungsten to citric acid was about 1:0.33.This portion was then dried at about 100° C. and labeled as catalyst 3c.A portion of catalyst 3c was treated in a flowing nitrogen stream (about200 cm³/min) in a quartz-lined tube furnace, with a heating rate ofabout 2° C./min, to a final temperature of about 320° C. and was held atthat temperature for about 90 minutes. It was then cooled toapproximately room temperature and removed from the furnace. It waslabeled as catalyst 3c//N₂.

FIG. 4 shows X-ray diffraction spectra of catalysts 3a and 3b and, bycomparison, the X-ray diffraction spectra of catalysts A and 2a. ThisFigure shows the partial conversion of the NiWO₄ hexagonal nickeltungstate oxide precursor phase upon addition of ethylenediamine to formtris-ethylenediamine nickel tungstate phase (catalyst 3a compared tocatalyst A), and the subsequent reversion of this phase on citric acidimpregnation (catalyst 3b) to the nickel tungstate oxide phase (catalyst2a).

FIG. 5 shows the X-ray diffraction spectra of catalysts 3a, 3a//N₂, 3b,3b//N₂, 3c, and 3c//N₂ after sulfidation, according to the protocoldescribed above, together with the X-ray diffraction spectrum of thesulfided NiWO₄ catalyst of Comparative Example 1 (indicated as A). FIG.5 shows that the (002) peak of the sulfide prepared from the neat oxide,the oxide impregnated with either en or citric alone, and the latter twowith inert high temperature treatment were all approximately equallysharp (i.e., they appear to have roughly the same width at half-heightfor the (002) reflection as the neat oxide precursor (6)). The sharpnessof the (002) peak is believed to correlate with increasing number ofstacks (and thus crystallite size) of tungsten sulfide. Clearly thesample with both the en and citric acid together exhibited a muchbroader (002) peak, whether with or without the high temperature N₂treatment.

Example 4 Preparation of NiWO₄/Citric Acid_(0.33)/(en)₁/N₂ andNiWO₄/Citric Acid_(0.33) Plus (en)₁/N₂

As in Example 3, the same hexagonal nickel tungstate oxide precursor(catalyst A) was used. The NiWO₄ was then impregnated with an aqueoussolution of citric acid, such that the molar ratio of tungsten to citricacid was about 1:0.33. This sample was then dried at about 100° C.,after which ethylenediamine (en, dissolved in water) was added (byincipient wetness) to a portion of this sample, such that the molarratio of en to citric acid was about 1:0.33 and such that the molarratio of tungsten to en was about 1:1. This sample was then dried againat about 100° C. and labeled as catalyst 4a. A portion of catalyst 4awas treated in a flowing nitrogen stream (about 200 cm³/min) in aquartz-lined tube furnace, with a heating rate of about 2° C./min, to afinal temperature of about 320° C. and was held at that temperature forabout 90 minutes. It was then cooled to approximately room temperatureand removed from the furnace. It was labeled as catalyst 4a//N₂.

A separate catalyst sample was prepared by combining the aqueous citricacid solution with ethylenediamine and by impregnating this solution (intwo incipient wetness steps) onto a portion of catalyst A, with dryingin air at about 100° C. after each impregnation step. It was labeled ascatalyst 4b. A portion of this sample was treated in a flowing nitrogenstream (about 200 cm³/min) in a quartz-lined tube furnace, with aheating rate of about 2° C./min, to a final temperature of about 320° C.and was held at that temperature for about 90 minutes. It was thencooled to approximately room temperature and removed from the furnace.It was labeled as catalyst 4b//N₂.

Portions of catalysts 4a//N₂ and 4b//N₂ were sulfided according to theprotocol described above. The X-ray diffraction spectra of the sulfidedsamples of catalysts 4a//N₂ and 4b//N₂ were compared to the spectrum ofsulfided catalyst 3b//N₂ in FIG. 6. FIG. 6 shows that, irrespective ofwhether the diamine impregnation is effected before, after, orsimultaneously with the organic acid impregnation, there appears to be asimilar broadening of the (002) peak.

Example 5 Preparation of Other Organic Promoted NiWO₄ Precursors

A variety of other samples, each containing both (i) a diamine or analkanolamine and (ii) an organic acid, impregnated onto the NiWO₄ oxideof Comparative Example 1 were prepared in a manner analogous to thedescription in Example 3. In each case, the amine was impregnated first,using the tungsten/amine mole ratio indicated in Table 1, followed bydrying at about 100° C., then a second impregnation of the organic acid,another drying at about 100° C., and then inert nitrogen treatment atabout 320° C.

TABLE 1 W/amine Organic W/acid Sample No. Amine mole ratio acid moleratio 5a//N₂ ethanolamine ~1 citric acid ~0.33 5b//N₂ o-phenylenediamine~1 citric acid ~0.33 5c//N₂ 1,4-diaminocyclohexane ~1 citric acid ~0.335d//N₂ 1,2-propylenediamine ~1 citric acid ~0.33 5e//N₂1,2-diaminocyclohexane ~1 citric acid ~0.33

Several other samples, each containing both (i) a monoamine or a diamineand (ii) an organic acid, impregnated onto the NiWO₄ oxide ofComparative Example 1 were prepared in a manner analogous to thedescription in Example 3. In each case, the amine was impregnated first,using the tungsten/amine mole ratio indicated in Table 2, followed bydrying at about 100° C., then a second impregnation of the organic acid,another drying at about 100° C., and then inert nitrogen treatment atabout 320° C.

TABLE 2 W/amine Organic W/acid Sample No. Amine mole ratio acid moleratio 5f//N₂ n-propylamine ~1 citric acid ~0.33 5g//N₂ Cyclohexylamine~1 citric acid ~0.33 5h//N₂ 1,3-propylenediamine ~1 citric acid ~0.33

Certain of the precursors shown in Tables 1 and 2 were sulfided asdescribed above, and the X-ray diffraction spectra of the resultantsulfides are shown in FIG. 7. It can be seen that the sulfides preparedfrom the monoamine precursors (propylamine and cyclohexylamine; 5f and5g respectively) exhibited sharper (002) peaks (at about 12-14 degrees2Θ). This indicated larger numbers of stacks than in the sulfidesprepared with the diamines, regardless of whether the diamine wascapable of forming bidentate coordinations (e.g., 1,2-propylenediamineand 1,2-diaminocyclohexane) or not (e.g., 1,3-propylenediamine and1,4-diaminocyclohexane).

Several further samples containing both amine and organic acidsimpregnated onto the NiWO₄ oxide were also prepared in a manneranalogous to the description in Example 3. These were prepared tocompare the behavior of different organic acids in the preparations. Ineach of these cases, the diamine was impregnated first, using thetungsten/amine mole ratio indicated in Table 3, followed by drying atabout 100° C., then a second impregnation of the organic acid, anotherdrying at about 100° C., and then inert nitrogen treatment at about 320°C. The precursors were sulfided as described above.

TABLE 3 W/diamine W/acid Sample No. Diamine mole ratio Organic acid moleratio 5k//N₂ ethylenediamine ~1 maleic acid ~0.50 5l//N₂ ethylenediamine~1.5 maleic acid ~0.75 5m//N₂ 1,2-propylenediamine ~1.5 maleic acid~0.75

Example 6 Preparation of Organic Promoted NiW_(0.975)Nb_(0.25)O₄Precursors

A different oxide precursor was used to prepare the dual promotedcatalysts. A sample of approximate nominal compositionNiW_(0.975)Nb_(0.025)O₄ was synthesized in a manner similar to thepreparation of NiWO₄ described in Comparative Example 1, except thatabout 2.5 mol % of the tungsten component (tungstic acid) wassubstituted with the appropriate molar amount of niobic acid. The X-raydiffraction spectrum of the resulting product was nearly identical tothe material without Nb, as shown in FIG. 8. The oxidic catalystprecursor containing Nb was designated as catalyst 6a. A portion ofcatalyst 6a was impregnated sequentially with ethylenediamine and thencitric acid, such that the mole ratios were as follows: [W+Nb]/en ofabout 1:1 and [W+Nb]/citric acid of about 1:0.33. The resultant productwas then treated in an inert nitrogen stream in the manner described inExample 3 and was labeled as catalyst 6b//N₂.

Example 7 Preparation of Organic Promoted CoW_(0.5)V_(0.5)O₄ Precursors

A sample of approximate nominal composition Co₁W_(0.5)V_(0.5) oxide wasprepared by reacting about 7.93 grams cobalt carbonate (about 0.067moles Co), about 3.03 grams vanadium oxide (V₂O₅; about 0.033 moles V),and about 8.33 grams tungstic acid (about 0.033 moles W) in a watersuspension of about 150 mL, while heating to about 150° C. for about 8hours. The resulting phase, identified as catalyst 7, exhibited an x-raydiffraction pattern shown in FIG. 9, where it is compared to the patternfor NiWO₄ of Comparative Example 1 (and also shown in FIG. 13). Aportion of catalyst 7 was used as the host oxide for sequentiallyimpregnation of ethylenediamine and then citric acid in a manneranalogous to the description in Example 3. The molar ratio of [W+V] toen was about 1:1, and the molar ratio of [W+V] to citric acid was about1:0.33. The samples were dried in air at about 100° C. after each of thetwo impregnation steps, thus forming catalyst 7a. A portion of thecatalyst 7a sample was then treated in a flowing nitrogen stream (about200 cm³/min) in a quartz-lined tube furnace, with a heating rate ofabout 2° C./min, to a final temperature of about 360° C. and was held atthat temperature for about 90 minutes. It was then cooled toapproximately room temperature and removed from the furnace. It waslabeled as catalyst 7a//N₂.

TESTING EXAMPLES

In Comparative Example 2 and Examples 8-14, catalyst activity resultswere obtained using a batch high-pressure reactor unit. The batchreactor was initially charged with about 65 μl of catalyst and about1.85 ml of sulfiding feed. A partially hydrotreated distillate feed(about 570 ppm sulfur content and about 350 ppm nitrogen content) wasused for sulfiding the catalyst. Catalyst sulfiding was done at about315° C. and at about 400 psig (about 2.9 MPag) using a hydrogen gasmixture containing about 10% H₂S for about 30 hours. The batch reactorassembly was orbitally shaken to ensure good mixing of the gas, liquid,and catalyst. Following sulfiding, the spent feed was removed byde-pressurizing the reactor and cooling the reactor assembly to ambientconditions (approximately room temperature, or about 20-25° C.). Tominimize air exposure, the feed removal and dispensing was performedinside a glove box kept under a nitrogen atmosphere. Catalystperformance was then evaluated by charging a fresh (1.85 ml) load ofvacuum gas oil (VGO) feed. The reactor was then pressurized to about 650psig (about 4.6 MPag) with ˜100% H₂ and heated to about 357° C. (about675° F.). The reaction was progressed for a total duration of about 24hours, following which the reactor was de-pressurized and cooled toambient conditions. The product liquid was sampled and analyzed fortotal nitrogen content using an Antek™ analyzer. In any given run,around 2-3 blank reactors loaded only with feed (no catalyst) were alsotested to set a baseline that was further used for calculating theactual catalyst activity. Because of the difficulty of accuratelydispensing the low volume of the solid catalysts, each catalyst wasweighed on an analytical balance, and the relative weight activitieswere determined using these weights.

The approximate nominal composition of the VGO used for the activitymeasurements in Examples 8-14 is shown in Table 4 below:

TABLE 4 Gravity, API ~21.4 Sulfur, wt % ~2.617 Nitrogen, wppm ~1005Basic Nitrogen, wppm ~270 Carbon, wt % ~86.0 Hydrogen, wt % ~9.6 Nickel,wppm ~0.23 Vanadium, wppm ~0.64 ConCarbon, wt % ~0.9 GC Distillation (wt%), ° F. IBP ~520 5 ~632 10 ~671 20 ~727 30 ~769 40 ~805 50 ~842 60 ~88370 ~934 80 ~1003 90 ~1074 95 ~1119 FBP ~1225 Saturates, wt % ~41.71-Ring Aromatics, wt % ~18.3 2-Ring Aromatics, wt % ~19.4 3-RingAromatics, wt % ~12.1 4-Ring Aromatics, wt % ~6.5 Polars, wt % ~2.1

Based on the liquid product analysis for N using the Antek™ analyzer,the catalyst performance was expressed in terms of relative weightactivity (RWA) with respect to a reference catalyst. The RWA for a givencatalyst was then calculated using the equation below:RWA=[ln(C ^(blank) /C ^(final))/(Cat. wt.)]/[ln(C ^(blank) /C^(final))/(Cat. wt.)]_(Ref)where C^(blank) represents the concentration (wppm) of total nitrogen inthe product liquid from a blank reactor after the activity run iscomplete, where C^(final) represents the final concentration of totalnitrogen (wppm) in the product liquid from a reactor containing thecatalyst, and where Cat. wt. represents the weight of the specificvolume of the catalyst dispensed. The reference catalyst used for allthe runs reported was a relatively high activity catalyst made from anoxide (only) catalyst precursor of approximate stoichiometryNiMo_(0.5)W_(0.5)O₄ (see catalyst B of Comparative Example 1).

Comparative Example 2 Testing of Catalysts of Comparative Example 1

The hydrodenitrogenation (HDN) activity of a sulfided sample of catalystA (bulk NiWO₄ with no organics present) for the VGO feed of Table 4 wascompared to that of a sulfided reference sample made from an oxide(only) catalyst precursor of approximate stoichiometryNiMo_(0.5)W_(0.5)O₄ (catalyst B). Catalyst A was found to have an RWA of1.02, indicating it to have practically the same HDN activity as thecatalyst B.

Example 8 Testing of Catalysts of Example 1

The HDN activity of sulfided samples of catalysts 1a, 1a//N₂, 1b, and1b//N₂, all of which were described in Example 1, were compared againstthe HDN activity of a sulfided reference sample made from catalyst B.The activities were normalized on a weight basis, relative to thereference, and are shown in Table 5. Because of the relatively lowdensity of these bimetallic oxide-amine hybrid phases, the activities ona relative volume basis were less than that of the reference catalyst.

TABLE 5 Sample Composition RWA 1a NiWO₄(1,2DACH)₂ ~1.07 1a//N₂NiWO₄(1,2DACH)₂//N₂ ~1.28 1b NiWO₄(1,2DACH)₂//citric_(0.33) ~0.60 1b//N₂NiWO₄(1,2DACH)₂//citric_(0.33)//N₂ ~1.18

Table 5 shows that the high temperature inert treatment of thebimetallic oxide-amine precursors, whether citric acid was impregnatedor not, improved their activity. The low density, and consequent lowervolumetric activity, of these Example 1 precursors tends to make themless preferred than the catalysts of Examples 2-7.

Example 9 Testing of Catalysts of Example 3

The HDN activity of sulfided samples of catalysts 3a, 3b, and 3b//N₂,all of which were described in Example 3, were compared against the HDNactivity of a sulfided reference sample made from catalyst B. Theactivities were normalized on a weight basis relative to the referenceand are shown in Table 6.

TABLE 6 Sample Composition RWA 3a Ni—W//en₁ (no citric) ~0.56 3bNi—W//en₁//citric_(0.33) ~0.74 3b//N₂ Ni—W//en₁//citric_(0.33)//N₂ treat~1.16

Table 6 shows that HDN activities higher than that of the referencecatalyst can be reached by having both the diamine and the organic acidpresent simultaneously, especially with the sample being treated in aninert stream at elevated temperature before sulfiding. Since thecatalyst with both the amine and citric acid treatment exhibited acrystal structure (see FIG. 4) of the mixed oxide (NiWO₄) with theorganic acid-salt coating its surface, the relatively high density ofthe oxide phase was maintained, and the relative volume activity wasalso higher than the reference.

Example 10 Testing of Nitrogen-Treated Catalysts of Examples 3 and 4

A sulfided sample of catalyst 3b//N₂ was selected together with a repeatsample preparation of same catalyst (catalyst 3b//N₂ repeat) and with asulfide sample of catalyst precursor 4a//N₂ (having the same compositionbut with the reverse sequence of addition, i.e., with citric acid addedfirst and then followed by ethylene diamine and subjected to the hightemperature nitrogen treatment). These three samples, along with asulfided reference sample made from catalyst B, were compared in a HDNactivity test using the vacuum gas oil described in Table 4. The resultsare shown in Table 7.

TABLE 7 Sample Composition RWA 3b//N₂ Ni—W//en₁//citric_(0.33)//N₂ treat~1.39 3b//N₂ repeat Ni—W//en₁//citric_(0.33)//N₂ treat ~1.29 4a//N₂Ni—W//citric_(0.33)//en₁//N₂ treat ~1.36

The data in Table 7 indicates that the sequence of addition of theethylene diamine and citric acid is not critical.

Example 11 Testing of Nitrogen-Treated Catalysts of Example 5

Sulfided samples of the catalyst precursors with different organic baseswere selected from preparations of Example 5 and were tested in an HDNtest using the vacuum gas oil of Table 4, together with a sulfidedreference sample made from catalyst B. The results are shown in Table 8.

TABLE 8 Sample Composition RWA 5a//N₂Ni—W//ethanolamine₁//citric_(0.33)//N₂ ~1.31 5b//N₂Ni—W//o-phenylendiamine₁//citric_(0.33)//N₂ ~1.38 5c//N₂ Ni—W//1,4diaminocyclohexane₁//citric_(0.33)//N₂ ~1.47 5d//N₂ Ni—W//1,2propylenediamine₁//citric_(0.33)//N₂ ~1.23 5e//N₂ Ni—W//1,2diaminocyclohexane₁//citric_(0.33)//N₂ ~1.33 5f//N₂Ni—W//n-propylamine₁//citric_(0.33)//N₂ ~1.21 5h//N₂ Ni—W//1,3propylenediamine₁//citric_(0.33)//N₂ ~1.41

The data in Table 8 shows that the promotion effect observed with thedual organics occurred with other diamines and also with anaminoalcohol. In addition, sample 5f//N₂, which contains propylamine,although it showed a higher number of stacks than the diamines as seenin FIG. 7, has only a marginally lower activity, indicating that eithermonoamines or diamines can be used as long as there was also a treatmentwith an organic acid and a subsequent inert treatment.

Example 12 Testing of Further Nitrogen-Treated Catalysts of Example 5

Sulfided samples of the catalyst precursors impregnated with maleic acidwere selected from preparations of Example 5 and were tested in an HDNtest using the vacuum gas oil of Table 4, together with a sulfidedreference sample made from catalyst B. The results are shown in Table 9.

TABLE 9 Sample Composition RWA 5k//N₂Ni—W//ethylenediamine₁//maleic_(0.50)//N₂ ~1.38 5l//N₂Ni—W//ethylenediamine_(1.5)//maleic_(0.75)//N₂ ~1.27 5m//N₂ Ni—W//1,2propylenediamine_(1.5)//maleic_(0.75)//N₂ ~1.33

The data in Table 9 shows that organic acids other than citric acid canalso be used to prepare active catalysts.

Example 13 Testing of Nitrogen-Treated Catalyst of Example 6

A sulfided sample of the niobium-containing precursor catalyst 6b//N₂was compared with a sulfided reference sample made from catalyst B in anHDN test using the vacuum gas oil of Table 4 and was found to have anRWA of about 1.53. This result shows that the addition of Nb to theprecursor Ni—W oxide can impart significant additional activity to theNi—W precursors prepared with the dual organic promotion.

Example 14 Testing of Catalysts of Example 7

Sulfided samples of catalyst 7 (approximate stoichiometryCo₁W_(0.5)V_(0.5) oxide only) and catalyst 7a//N₂ (approximatestoichiometry Co₁W_(0.5)V_(0.5) oxide impregnated with ethylenediamineand citric acid and heated in nitrogen) were compared with a sulfidedreference sample made from catalyst B in an HDN test using the vacuumgas oil of Table 4. The results are shown in Table 10.

TABLE 10 Sample Composition RWA 7 Co₁V_(.5)W_(.5) ~0.72 7a//N₂Co₁V_(.5)W_(.5)//ethylenediamine₁//citric_(.33)//N₂ ~1.65

Table 10 shows that this composition containing cobalt, vanadium, andtungsten with the dual organic promoters and high temperature inerttreatment was more active than the host oxide catalyst and exceeded theactivity of the reference material.

Example 15 Flow Reactor Testing of Catalysts of Example 5

In this Example, catalyst activity results were obtained using a threephase flow reactor test. Each of the three reactors used in the test wasa stainless steel U-shaped vessel having a ˜0.28 inch (˜0.7 cm) internaldiameter, with quartz wool at the inlet and quartz wool and a glassfitted gasket at the exit. Each of the three reactors was loaded with adifferent catalyst precursor to be tested and was placed in a commonsand bath and run in an up-flow mode. The catalyst precursors employedin the tests were: (a) sample 5b//N₂(NiWO₄//o-phenylendiamine₁//citric_(0.33)//N₂ treated at about 320° C.),(b) sample 5g//N₂ (NiWO₄//cyclohexylamine₁//citric acid_(0.33)//N₂treated at about 320° C.), and (c) the reference catalyst, catalyst B,(approximate stoichiometry Ni₁Mo_(0.5)W_(0.5)O₄). Each of the sampleswas pilled, crushed, and sieved to ˜35/60 mesh (˜250-500 μm), and thenmixed with ˜40-60 mesh quartz powder, to give a total volume of about 6cc, with half the volume comprising the catalyst precursor and half thequartz diluent.

After the charged reactors were pressure-tested for about 4 hours withN₂ at about 400 psig (about 2.9 MPag) outside the sand bath and with H₂at about 1250 psig (about 8.72 MPag) inside the sand bath, the pressurewas lowered to around atmospheric pressure, and, with the H₂ flowing atabout 48 sccm, the temperature was raised to about 100° C. At about 100°C., the pressure was set to about 100 psig (about 790 kPa), H₂ flow wasstopped, and the sulfiding feed (about 7.5 wt % dimethyl disulfide,dissolved in a diesel boiling range stream) was flowed at about 8 ml/hrover each catalyst for about 4 hours. Then, with the sulfiding feedcontinuing, H₂ was added to each reactor at a flow rate of about 48sccm, the pressure was raised to about 650 psig (about 4.6 MPag), andthen the temperature was increased to about 235° C. over about 4 hours.The system was then kept isothermal at about 235° C. for about another12 hours. Following that isothermal treatment, the temperature wasraised to about 345° C. over a period of about 4.5 hours and wasisothermally held for about another 16 hours. This completed thesulfiding of the catalyst.

The temperature was then cooled to about 230° C. over an ˜8 hour period,and the sulfiding feed was then replaced by the vacuum gas oil (VGO)specified below in Table 11. The feed vessels, ISCO pumps, reservoirs,and all the unit lines were heated to ˜80-120° C. to keep the VGO feedflowing. The pressure was raised to about 1200 psig (about 8.4 MPag) andthe temperature increased from about 230° C. to about 365° C. over aperiod of about 4 hours. The VGO flow was set at about 3.3 ml/hr, andthe H₂ flow rate was set to about 49.5 sccm. This was roughly equivalentto an LHSV of about 1 hr⁻¹ and a hydrogen flow of about 5000 scf/bbl.After about 18-24 hours, the first liquid samples were obtained, andsampling was continued once a day for the remainder of the run. Acalibrated ANTEK™ 9000 series analyzer was used to measure the sulfurand nitrogen content of the diluted product.

TABLE 11 Gravity, API ~21.6 Sulfur, wt % ~1.464 Nitrogen, wppm ~1614Specific Gravity, g/cm³ ~0.924 GC Distillation (wt %), ° F. IBP ~496 10~663 30 ~768 50 ~839 70 ~913 90 ~1007 95 ~1048 Saturates, wt % ~43.31-Ring Aromatics, wt % ~18.6 2-Ring Aromatics, wt % ~15.4 3-RingAromatics, wt % ~10.7 Total Aromatics, wt % ~44.7

The results for the relative volumetric activities (RVAs) of thecatalysts for hydrodenitrogenation of the VGO feed are shown in FIG. 10,assuming ˜1.25 order in nitrogen.

Example 16 Preparation of NiWO₄//(Oleylamine)_(0.23)(air 250° C.)/CitricAcid_(0.19)(Air 230° C.)//N₂ 320° C.

The NiWO₄ from Example 1 was impregnated with oleylamine (70% technicalgrade, commercially available from Aldrich of Milwaukee, Wis.), suchthat the mole ratio of NiWO₄ to oleylamine was about 1:0.23. The samplewas first dried at about 100° C. overnight in a drying oven and was thenplaced in a box furnace, which was programmed at a ramp rate of about 2°C./min up to about 250° C. The sample was held at that temperature forabout 4 hours in stagnant air. This sample was then impregnated with anaqueous citric acid solution, such that the NiWO₄ to citric acid moleratio was about 1:0.19. This sample was again dried at about 100° C.overnight in a drying oven and was then placed in a box furnace in air,which was programmed at a ramp rate of about 2° C./min up to about 230°C. The sample was held at that temperature for about 4 hours and wasthen placed in a quartz line tube furnace and heated in a flowingnitrogen stream (about 300 cm³/min) with a heating rate of about 2°C./min to a final temperature of about 320° C. The sample was held atthat temperature for about 90 minutes and was then cooled toambient/room temperature and removed from the furnace. It was labeled ascatalyst C.

Example 18 Preparation of NiWO₄//Aniline₁//Citric Acid_(0.33)//N₂ 320°C.

The NiWO₄ from Example 1 was impregnated with aniline (ACS reagent,99.5%, commercially available from Aldrich of Milwaukee, Wis.), suchthat the mole ratio of NiWO₄ to aniline was about 1:1. The sample wasplaced into a drying oven and maintained at about 100° C. overnight. Thesample was then impregnated with an aqueous citric acid solution, suchthat the NiWO₄ to citric acid mole ratio was about 1:0.33. This samplewas again dried at about 100° C. overnight in a drying oven and was thenheated in a flowing nitrogen stream (about 300 cm³/min) in a quartz linetube furnace with a heating rate of about 2° C./min to a finaltemperature of about 320° C. The sample was held at that temperature forabout 90 minutes and was then cooled to ambient/room temperature andremoved from the furnace. It was labeled as catalyst D.

Example 19 Preparation of NiWO₄//(Oleylamine)_(0.13)/(CitricAcid)_(0.15)//Air 230° C.

The NiWO₄ from Example 1 was impregnated with oleylamine (70% technicalgrade, commercially available from Aldrich of Milwaukee, Wis.), suchthat the mole ratio of NiWO₄ to oleylamine was about 1:0.13. The samplewas placed into a drying oven and maintained at about 100° C. overnight.The sample was then impregnated with an aqueous citric acid solution,such that the NiWO₄ to citric acid mole ratio was about 1:0.15. Thissample was again dried at about 100° C. overnight in a drying furnaceand was then placed in a box furnace in air and heated at a rate ofabout 0.5° C./min to a final temperature of about 230° C. The sample washeld at that temperature for about 4 hours and was then cooled toambient/room temperature and removed from the furnace. It was labeled ascatalyst E.

Example 20 Preparation NiWO₄//(Oleylamine)_(0.13)/(CitricAcid)_(0.15)//N₂ 320° C.

The NiWO₄ from Example 1 was impregnated with oleylamine (70% technicalgrade, commercially available from Aldrich of Milwaukee, Wis.), suchthat the mole ratio of NiWO₄ to oleylamine was about 1:0.13. The samplewas placed into a drying oven and maintained at about 100° C. overnight.The sample was then impregnated with an aqueous citric acid solution,such that the NiWO₄ to citric acid mole ratio was about 1:0.15. Thissample was again dried at about 100° C. overnight in a drying furnaceand was then placed in a box furnace and heated in a flowing nitrogenstream (about 400 cm³/min) in a quartz line tube furnace with a heatingrate of about 2° C./min to a final temperature of about 320° C. Thesample was held at that temperature for about 90 minutes and was thencooled to ambient/room temperature and removed from the furnace. It waslabeled as catalyst F.

The organic contents of the different samples, obtained bythermogravimetric measurements, are listed below in Table 12.

TABLE 12 Approximate organic content after impregnation CatalystPrecursor and indicated thermal treatment of precursor (%) A 0 C 15.8 D12.7 E 15.8 F 11.8

The catalyst precursors compositions were sulfided, as described above,and their sulfided XRD spectra are shown in FIG. 11 (the spectrum forCatalyst A is shown in FIG. 1, and its synthesis was described inComparative Example 1 herein). The sulfided sample prepared usinganiline as the first organic compound exhibited only a slighter broader(002) peak than the samples obtained using propylamine andcyclohexylamine as the first organic compound (Samples 5f and 5g,respectively). The samples prepared using oleylamine as the firstorganic (Catalysts C, E, and F) compound show measurably broader (002)peaks, indicating notably smaller numbers of stacks and thus notablysmaller crystallites.

Catalysts A and C—F were compared in two different three phase flowreactor tests using a VGO feed. The VGO used in test had the propertiesshown below in Table 11 hereinabove.

Each of the powdered catalyst samples were pilled, crushed, and sievedto approximately 35/60 mesh (about 250-500 μm diameter), and then mixedwith ˜40-60 mesh quartz powder to give a total volume of about 6 cm³,with roughly half of the volume comprising the catalyst sample androughly half the quartz diluent. Each sample was loaded into a stainlesssteel U-shaped reactor (˜0.71 cm diameter) with quartz wool at the inletand quartz wool and a glass fritted gasket at the exit. Each of threereactors was placed in a common sand bath and run in an up-flow mode.After the charged reactors were pressure-tested for about 4 hours withnitrogen at about 400 psig (about 2.8 MPag) outside the sand bath andwith hydrogen at about 1250 psig (about 8.62 MPag) inside the sand bath,the pressure was lowered to approximately atmospheric pressure. Then,with the hydrogen flowing at about 48 Scm³/min (sccm), the temperaturewas raised to about 100° C. At about 100° C., the pressure was increasedto about 100 psig (about 690 kPag), hydrogen flow was stopped, and thesulfiding feed (about 7.5 wt % dimethyl disulfide, or DMDS, dissolved ina diesel boiling range feed) flowing at a rate of about 8 mL/hr waspassed over each sample for about 4 hours. Then, with the sulfiding feedcontinuing, hydrogen was added to each reactor with a flow rate of about48 sccm, at which point the pressure was raised to about 650 psig (about4.5 MPag) and then the temperature was increased to about 235° C. overabout the next 4 hours. The system was then held at approximatelyisothermal conditions at about 235° C. for about another 12 hours.Following that isothermal treatment, the temperature was raised again toabout 345° C. over a period of about 4.5 hours and held at approximatelyisothermal conditions for about another 16 hours, at which pointcatalyst sulfidation was considered complete.

The temperature was then cooled to about 230° C. over about an 8 hourperiod, and the sulfiding feed was replaced by the vacuum gas oil (VGO).The feed vessels, ISCO pumps reservoirs, and all the unit lines wereheated to about 80-120° C. to facilitate flow of the VGO (e.g., to putthe VGO in a liquid state). The pressure was then raised to about 1200psig (about 8.3 MPag) and the temperature increased from about 230° C.to about 365° C. over a period of about 4 hours. VGO flow was set atabout 3.3 mL/hr, and the hydrogen flow rate was set to about 49.5 sccm,which was equivalent to an LHSV of about 1.1 hr⁻¹ and a hydrogen flow ofabout 5000 scf/bbl (about 845 Sm³/m³). After about 18-24 hours, thefirst liquid samples were obtained, and sampling was continued once aday for the remainder of the run. A calibrated ANTEK 9000 seriesinstrument was used to measure the sulfur and nitrogen content of thediluted product. Catalysts A, C, and D were compared after about 20 dayson stream. The nitrogen and sulfur contents are shown in Table 13.

TABLE 13 Catalyst Days on stream N ppm S ppm A 20 209 250 C 20 76 86 D20 86 90

Catalysts A, E, and F were compared in a similar feed under similarconditions. After about 29 days on stream, the nitrogen and sulfurcontents in the product, as well as the RVAs and RMAs based on HDNactivity, were obtained and are shown in Table 14.

TABLE 14 Catalyst Days on stream N ppm S ppm RVA RMA A 29 321 356 1.001.00 E 29 69 64 1.75 1.59 F 29 304 337 1.09 0.90

Infrared spectra were obtained for a series of catalyst precursorsincluding Catalyst Precursors E and F (NiWO₄//(oleylamine)_(0.13)/citricacid_(0.15)/air 230° C. and NiWO₄//(oleylamine)_(0.13)/citricacid_(0.15)/N₂ 320° C., respectively), where the treatment temperaturewas varied from about 100° C. to about 230° C. in air and to about 320°C. in nitrogen (pre-sulfidation). The results are shown in FIG. 12.

Example 21 Preparation of NiWO₄//(Oleylamine)_(0.1)/(OleicAcid)_(0.06)//Air 220° C.

The NiWO₄ from Example 1 was impregnated with oleylamine (70% technicalgrade, commercially available from Aldrich of Milwaukee, Wis.), suchthat the mole ratio of NiWO₄ to oleylamine was about 1:0.10. The samplewas placed into a drying oven and maintained at about 100° C. overnight.The sample was then impregnated with oleic acid (90% technical grade,commercially available from Aldrich of Milwaukee, Wis.), such that theNiWO₄ to oleic acid mole ratio was about 1:0.06. This sample was againdried at about 100° C. overnight in a drying furnace and was then placedin a box furnace in air and heated at a rate of about 0.5° C./min to afinal temperature of about 220° C. The sample was held at thattemperature for about 4 hours and was then cooled to ambient/roomtemperature and removed from the furnace. It was labeled as catalyst G.The approximate organic content of Catalyst G (before sulfidation) wasfound to be about 17.4%.

Another run was performed with the same VGO feed from Table 11 herein inthe same manner as in Example 20 at the following conditions: atemperature of about 365° C., a total pressure of about 1200 psig (about8.3 MPag), a hydrogen treat gas rate of about 5000 scf/bbl (about 845Sm³/m³), and a weight hourly space velocity (WHSV) of about 1.1 hr⁻¹.The HDN and HDS capability of Catalysts A, E, and G were compared afterabout 23 days on stream. The nitrogen and sulfur contents were obtainedand are shown in Table 15 below. Following a change in conditions todecrease the pressure (to about 800 psig, or about 5.5 MPag) and spacevelocity (down to about 0.73 hr⁻¹), the sulfur and nitrogen contentsafter about 34 days on stream were obtained and are shown in Table 16below.

TABLE 15 Catalyst Precursor Days on stream N ppm S ppm A 23 330 329 E 2357 49 G 23 57 46

TABLE 16 Catalyst Precursor Days on stream N ppm S ppm A 34 271 146 E 3475 30 G 34 84 27

Example 22 Preparation of NiWO₄//(Oleylamine)_(0.13)//Air 230° C.

The NiWO₄ from Example 1 was impregnated with oleylamine (70% technicalgrade, commercially available from Aldrich of Milwaukee, Wis.), suchthat the mole ratio of NiWO₄ to oleylamine was about 1:0.13. The samplewas placed into a drying furnace and maintained at about 100° C.overnight. This sample was then heated in air at a rate of about 0.5°C./min to a final temperature of about 230° C. The sample was held atthat temperature for about 4 hours and was then cooled to ambient/roomtemperature and removed from the furnace. It was labeled as catalyst H.The approximate organic content of Catalyst H (before sulfidation) wasfound to be about 12.2%.

Example 23 Preparation of NiWO₄//(Oleic Acid)_(0.13)//Air 220° C.

The NiWO₄ from Example 1 was impregnated with oleic acid (90% technicalgrade, commercially available from Aldrich of Milwaukee, Wis.), suchthat the mole ratio of NiWO₄ to oleic acid was about 1:0.13. The samplewas placed into a drying furnace and maintained at about 100° C.overnight. This sample was then heated in air at a rate of about 0.5°C./min to a final temperature of about 220° C. The sample was held atthat temperature for about 4 hours and was then cooled to ambient/roomtemperature and removed from the furnace. It was labeled as catalyst J.The approximate organic content of Catalyst J (before sulfidation) wasfound to be about 14.7%.

Another run was performed with the same VGO feed from Table 11 herein inthe same manner as in Example 20 at the following conditions: atemperature of about 365° C., a total pressure of about 1200 psig (about8.3 MPag), a hydrogen treat gas rate of about 5000 scf/bbl (about 845Sm³/m³), and a weight hourly space velocity (WHSV) of about 1.1 hr⁻¹.The HDN and HDS capability of Catalysts A, H, and J were compared afterabout 19 days on stream. The nitrogen and sulfur contents, as well asthe relative volume and molar HDN activities, were obtained and areshown in Table 17 below.

TABLE 17 Catalyst Precursor Days on stream N ppm S ppm RVA RMA A 19 315339 1.00 1.00 H 19 114 80 1.62 1.55 J 19 110 92 1.63 1.43

These results show that the catalysts treated with both the first andsecond organic compounds, namely the combination of oleylamine and oleicacid (e.g., Catalysts E and G, as shown in Table 15) are more activethan the catalysts treated with either the first or second organiccompound, namely oleylamine alone or oleic acid alone (e.g., Catalysts Hand J, as shown in Table 17), when treated under similar conditions andsubject to a hydrocarbon (in these cases, VGO) feed.

Example 24 Preparation of Oxide Precursors CoWO₄, CoMoO₄,Co_(1.5)MoO_(4.5), and Co_(2.5)MoO_(5.5) (No Organics)

The CoWO₄ precursor sample was formed by a solid-slurry reaction betweencobalt carbonate and tungstic acid. About 23.79 grams of cobaltcarbonate and about 49.97 grams of tungstic acid were added to about 800mL of water to form a suspension (pH≈6.4) that was placed into a ˜1 Lround bottom flask equipped with a condenser, which was then heated toabout 90° C. for about 16 hours. After cooling to ambient/roomtemperature, the solid was filtered and dried overnight at about 100° C.in a drying oven. FIG. 13 shows the XRD spectrum of this sample.

The Co₁Mo₁O₄ precursor sample was prepared by reacting about 23.78 gramsof cobalt carbonate with about 28.8 grams of MoO₃ slurried in ˜800 mL ofwater. This mixture was placed into a ˜1 L round bottom flask equippedwith a condenser, which was then heated to about 90° C. for about 16hours. After cooling to ambient/room temperature, the solid was filteredand dried overnight at about 100° C. in a drying oven. FIG. 13 shows theXRD spectrum of this sample.

The Co_(2.5)Mo₁O_(5.5) precursor sample was prepared by reacting about59.5 grams of cobalt carbonate with about 28.8 grams of MoO₃ slurried in˜800 mL of water. This mixture was placed into a ˜1 L round bottom flaskequipped with a condenser, which was then heated to about 90° C. forabout 16 hours. After cooling to ambient/room temperature, the solid wasfiltered and dried overnight at about 100° C. in a drying oven. FIG. 13shows the XRD spectrum of this sample.

The Co_(1.5)Mo₁O_(4.5) precursor sample (containing ammonium ions) wasprepared by first dissolving about 17.65 grams of ammoniumheptamolybdate tetrahydrate (about 0.1 mole Mo) in ˜800 mL of water andplacing this into a ˜1 L round bottom flask equipped with a condenser.To this solution, about 22.5 mL of concentrated NH₄OH (˜3:1 mole ratioof NH₄OH/Co) was added, thus raising the pH to ˜9.4 (solution A). Thissolution was then warmed to about 90° C. A second solution was preparedby dissolving about 43.64 grams of cobalt nitrate hexahydrate, (about0.15 moles Co) in about 50 mL of water (solution B) and maintaining thissolution at a temperature of about 90° C. The cobalt solution (solutionB) was added dropwise at a rate of about 7 cm³/min into the molybdenumsolution (solution A). A precipitate began to form after about ¼ of thesolution was added. The final pH after solutions A and B were mixedtogether was ˜6.5. This suspension/slurry was stirred for an additional30 minutes while the temperature was maintained at 90° C., after whichit was cooled to ambient/room temperature, filtered, and dried at about120° C. The total weight after drying was about 30.2 grams. The XRDspectrum of the dried sample is shown in FIG. 13.

Example 25 Preparation of CoV_(0.5)W_(0.5)O₄/(Oleylamine)_(0.67)/(OleicAcid)_(0.094)//Air 170° C.

The CoV_(0.5)W_(0.5)O₄ precursor sample from Example 7 was impregnatedwith oleylamine (70% technical grade, commercially available fromAldrich of Milwaukee, Wis.), such that the mole ratio ofCoV_(0.5)W_(0.5)O₄ to oleylamine was about 1:0.067. The sample wasplaced into a drying furnace and maintained at about 100° C. overnight.This sample was then impregnated with oleic acid (90% technical grade,commercially available from Aldrich of Milwaukee, Wis.), such that theCoV_(0.5)W_(0.5)O₄ to oleic acid mole ratio was about 1:0.094. Thissample was then dried at about 100° C. overnight, followed by heating ina box furnace in air at a rate of about 0.5° C./min to a finaltemperature of about 170° C. The sample was held at that temperature forabout 2 hours and was then cooled to ambient/room temperature beforebeing removed from the furnace.

Example 26 Preparation of CoWO₄/(Oleylamine)_(0.13)/(CitricAcid)_(0.15)//Air 10° C.

The CoWO₄ precursor sample from Example 24 was impregnated witholeylamine (70% technical grade, commercially available from Aldrich ofMilwaukee, Wis.), such that the mole ratio of CoWO₄ to oleylamine wasabout 1:0.13. The sample was placed into a drying furnace and maintainedat about 100° C. overnight. This sample was then impregnated with anaqueous citric acid solution, such that the CoWO₄ to citric acid moleratio was about 1:0.15. This sample was then dried at about 100° C.overnight, followed by heating in a box furnace in air at a rate ofabout 0.5° C./min to a final temperature of about 210° C. The sample washeld at that temperature for about 2 hours and was then cooled toambient/room temperature before being removed from the furnace.

Example 27 Preparation of CoMoO₄/(Oleylamine)_(0.059)/(OleicAcid)_(0.075)//Air 200° C.

The CoMoO₄ precursor sample from Example 24 was impregnated witholeylamine (70% technical grade, commercially available from Aldrich ofMilwaukee, Wis.), such that the mole ratio of CoMoO₄ to oleylamine wasabout 1:0.059. The sample was placed into a drying furnace andmaintained at about 100° C. overnight. This sample was then impregnatedwith oleic acid (90% technical grade, commercially available fromAldrich of Milwaukee, Wis.), such that the CoWO₄ to oleic acid moleratio was about 1:0.075. This sample was then dried at about 100° C.overnight, followed by heating in a box furnace in air at a rate ofabout 0.5° C./min to a final temperature of about 200° C. The sample washeld at that temperature for about 2 hours and was then cooled toambient/room temperature before being removed from the furnace.

Example 28 Preparation of Co_(1.5)MoO_(4.5)/(Oleylamine)_(0.067)/(OleicAcid)_(0.085)//Air 170° C. or 200° C.

The Co_(1.5)MoO_(4.5) precursor sample from Example 24 was impregnatedwith oleylamine (70% technical grade, commercially available fromAldrich of Milwaukee, Wis.), such that the mole ratio of Co_(1.5)MoO₄₅to oleylamine was about 1:0.067. The sample was placed into a dryingfurnace and maintained at about 100° C. overnight. This sample was thenimpregnated with oleic acid (90% technical grade, commercially availablefrom Aldrich of Milwaukee, Wis.), such that the Co_(1.5)MoO_(4.5) tooleic acid mole ratio was about 1:0.085. This sample was then dried atabout 100° C. overnight, followed by heating in a box furnace in air ata rate of about 0.5° C./min to a final temperature of either about 170°C. or about 200° C. For either heating temperature, the samples wereheld at that temperature for about 2 hours and were then cooled toambient/room temperature before being removed from the furnace.

Example 29 Preparation of Co_(2.5)MoO_(5.5)/(Oleylamine)_(0.074)/OleicAcid_(0.095)//Air 200° C.

The Co_(2.5)MoO_(5.5) precursor sample from Example 24 was impregnatedwith oleylamine (70% technical grade, commercially available fromAldrich of Milwaukee, Wis.), such that the mole ratio ofCo_(1.5)MoO_(4.5) to oleylamine was about 1:0.067. The sample was placedinto a drying furnace and maintained at about 100° C. overnight. Thissample was then impregnated with oleic acid (90% technical grade,commercially available from Aldrich of Milwaukee, Wis.), such that theCo_(2.5)MoO_(5.5) to oleic acid mole ratio was about 1:0.095. Thissample was then dried at about 100° C. overnight, followed by heating ina box furnace in air at a rate of about 0.5° C./min to a finaltemperature of about 200° C. The sample was held at that temperature forabout 2 hours and was then cooled to ambient/room temperature beforebeing removed from the furnace.

Example 30 Hydroprocessing Testing Comparison for Catalyst Samples

The catalysts made according to Examples 25, 27, 28, and 29, as well asa reference catalyst (CoMo supported on alumina; commercially availablefrom Albemarle of Baton Rouge, La.), were sulfided using the followingprocedure. After loading each catalyst sample into a reactor vessel,with ˜100% pure hydrogen flowing at about 1250 scf/bbl (about 213Nm³/m³), the temperature was raised to about 107° C. at a rate of about14° C./hr. At about 107° C. and at a pressure of about 380 psig (about2.6 MPag), the sulfiding feed (dimethyl disulfide, or DMDS, dissolved ina diesel boiling range feed to attain a sulfur content of about 2.6%)flowing at a rate sufficient to attain an LHSV of about 1.0 hr⁻¹ waspassed through each sample for about 5 hours. Then, with the sulfidingand hydrogen feeds continuing to flow, the temperature was raised toabout 232° C. at a rate of about 14° C./hr and held at approximatelyisothermal conditions for about 20 hours. Following that isothermaltreatment, the temperature was raised again to about 321° C. at a rateof about 14° C./hr and held at approximately isothermal conditions forabout 12 hours, followed by another temperature increase to about 343°C. at a rate of about 14° C./hr and held at approximately isothermalconditions for about 8 hours, at which point catalyst sulfidation wasconsidered complete.

Further, in these experiments, the reaction conditions were as follows:a temperature of about 655° F. (about 346° C.) EIT, a total pressure ofabout 575 psig (about 3.97 MPag), an LHSV of about 0.85 hr⁻¹, and ahydrogen treat gas rate of about 936 scf/bbl (about 159 Nm³/m³). Thesesulfided catalysts were used to hydroprocess a diesel boiling range feedhaving the following properties: a sulfur content of about 1.37 wt %; anitrogen content of about 134 wppm; an API gravity of about 33.1(degrees); and a T₉₅ of about 709° F. (about 376° C.). The sulfurcontents of the hydroprocessed diesel boiling range products after about20 days on stream were obtained and are shown in Table 18 below.

TABLE 18 Catalyst Product Sulfur (ppm) Reference catalyst 31 Example 25330 Example 27 95 Example 28* 18 Example 29 31 *170° C. treatmenttemperature

As can be seen from the product sulfur levels in the table above, thecatalyst made according to Example 28 exhibited the lowest productsulfur, which can correlate to the highest relative hydrodesulfurization(HDS) activity (since all other reaction and feed conditions wereconstant).

Example 31 Catalyst Performance on Mixed Biofeed

Three catalysts were compared in a three phase flow reactor test using apredominantly VGO feed, which contained about 20 wt % soybean oil.Catalyst K was a commercially available NiMo catalyst supported onalumina. Catalyst L was a commercially available bulk NiMoW catalyst.Catalyst M was a catalyst according to the invention, with similarcomposition to Catalysts E and/or G. The soybean oil was substantiallyfree of sulfur, nitrogen, and metal heteroatoms and comprisedpredominantly triglycerides with varying alkyl chain lengths, but mostlyC₁₈. The VGO base used in this Example exhibited the propertiesdelineated in Table 19 below.

TABLE 19 Feed Sulfur, wt % ~2.60 Feed Nitrogen, wppm ~828 Feed Density@~70° C., g/mL ~0.885 Distillation, ° C. IBP ~299 10 wt % ~368 30 wt %~408 50 wt % ~436 70 wt % ~463 90 wt % ~497 95 wt % ~510 Saturates, wt %~43 Aromatics, wt % ~50 1-ring aromatics, wt % ~14 2-ring aromatics, wt% ~16 3-ring aromatics, wt % ~13 4-ring aromatics, wt % ~7

The Catalysts were sulfided using a procedure similar to that describedin Example 20 herein. Further, in these experiments, the reactionconditions were as follows: a temperature of about 680° F. (about 360°C.) EIT, a total pressure of about 1287 psig (about 8.87 MPag), and ahydrogen treat gas rate of about 5950 scf/bbl (about 1010 Nm³/m³).Catalyst K was run at an LHSV of about 0.77 hr⁻¹, while Catalysts L andM were each run at LHSV values of about 1.08 hr⁻¹. The nitrogen andsulfur contents after about 78 days on stream were obtained and areshown in Table 20 below.

TABLE 20 Catalyst Days on stream N ppm S ppm K 78 51 446 L 78 27 163 M78 15 62

The liquid product obtained was substantially oxygen free, with greaterthan 99% removal of oxygen. The oxygen was removed in various forms,e.g., as water, CO, and/or CO₂. Table 21 shows the H₂S-freeconcentrations of these side-products in the reactor gas effluentstream.

TABLE 21 Catalyst Days on stream CO wt % CO₂ wt % K 78 3.2 3.4 L 78 4.55.9 M 78 2.2 6.6

Example 32 Catalyst Performance on Mixed Biofeed

Catalysts K, L, and M were compared in a three phase flow reactor testusing a predominantly gasoil feed, which contained about 20 wt % soybeanoil. The soybean oil was the same as in Example 31, but the gasoil baseused in this Example exhibited the properties delineated in Table 22below.

TABLE 22 Feed Sulfur, wt % ~1.79 Feed Nitrogen, wppm ~383 Feed APIGravity, degrees ~31.0 Distillation, ° F. IBP ~305 10 wt % ~542 30 wt %~615 50 wt % ~647 70 wt % ~677 90 wt % ~715 95 wt % ~723 Saturates, wt %~67.3 Aromatics, wt % ~32.7 1-ring aromatics, wt % ~20.8 2-ringaromatics, wt % ~10.2 3-ring aromatics, wt % ~1.8

The Catalysts were sulfided using a procedure similar to that describedin Example 20 herein. Further, in these experiments, the reactionconditions were as follows: a temperature of about 625° F. (about 329°C.) EIT, a total pressure of about 1000 psig (about 6.9 MPag), and atreat gas rate of about 2070 scf/bbl (about 350 Nm³/m³). Catalyst K wasrun at an LHSV of about 0.78 hr⁻¹, while Catalysts L and M were each runat LHSV values of about 1.11 hr⁻¹. The nitrogen and sulfur contentsafter about 78 days on stream were obtained and are shown in Table 23below.

TABLE 23 Catalyst Days on stream N ppm S ppm K 84 42 1288 L 84 17 743 M84 9 437

The liquid product obtained was substantially oxygen free, with greaterthan 99% removal of oxygen. The oxygen was removed in various forms,e.g., as water, CO, and/or CO₂. Table 24 shows the H₂S-freeconcentrations of these side-products in the reactor gas effluentstream.

TABLE 24 Catalyst Days on stream CO wt % CO₂ wt % K 84 0.81 1.40 L 84 —— M 84 1.54 1.22

Example 33 Catalyst Performance in Hydrocracking Function

Catalysts K, L, and M were compared in a three phase flow reactor testusing two different VGO feeds, labeled VGO1 and VGO2. The VGO feeds usedin this Example exhibited the properties delineated in Table 25 below.

TABLE 25 Property VGO1 VGO2 Feed Sulfur, wt % ~2.64 ~2.96 Feed Nitrogen,wppm ~690 ~1510 Feed API Gravity, degrees ~21.8 ~17.8 Distillation, ° F.IBP ~595 ~700 10 wt % ~706 ~845 30 wt % ~748 ~926 50 wt % ~822 ~975 70wt % ~845 ~1038 90 wt % ~923 ~1104 95 wt % ~946 ~1146 FBP ~1003 ~1164

The Catalysts were sulfided using a procedure similar to that describedin Example 20 herein. Further, in these experiments, the reactionconditions were varied. The nitrogen and sulfur contents after about 40days on stream were obtained for VGO1 feed at the following conditions:a temperature of about 710° F. (about 377° C.) EIT, an LHSV of about 1.4hr⁻¹, and a hydrogen treat gas rate of about 4000 scf/bbl (about 680Nm³/m³). Catalyst K was run at a total pressure of about 1875 psig(about 12.9 MPag), while Catalysts L and M were each run at a totalpressure of about 1275 psig (about 8.8 MPag). Results are shown in Table26 below, which indicate superior performance of the treated catalystcomposition, even at relatively lower pressures.

TABLE 26 Catalyst Days on stream N ppm S ppm K 40 <10 1959 L 40 <10 501M 40 <10 163

Then, the nitrogen and sulfur contents after about 69 days on streamwere obtained for VGO1 feed at the following conditions: a temperatureof about 710° F. (about 377° C.) EIT, a total pressure of about 1875psig (about 12.2 MPag), and a hydrogen treat gas rate of about 4000scf/bbl (about 680 Nm³/m³). Catalysts L and M were each run at an LHSVof about 2.3 hr⁻¹, while Catalyst K was run at an LHSV of about 1 hr⁻¹.Results are shown in Table 27 below, which indicate superior performanceof the treated catalyst composition, even at relatively higher spacevelocities.

TABLE 27 Catalyst Days on stream N ppm S ppm K 69 <10 34 L 69 <10 47 M69 <10 23

Thereafter, the nitrogen and sulfur contents after about 74 days onstream were obtained for VGO2 feed at the following conditions: atemperature of about 710° F. (about 377° C.) EIT, a total pressure ofabout 1875 psig (about 12.2 MPag), an LHSV of about 2 hr⁻¹, and ahydrogen treat gas rate of about 4000 scf/bbl (about 680 Nm³/m³).Results are shown in Table 28 below, which indicate superior performanceof the treated catalyst composition, even for heavier/more refractoryfeeds.

TABLE 28 Catalyst Days on stream N ppm S ppm K 74 589 3225 L 74 226 1315M 74 158 776

Example 34 Preparation ofNiMo_(0.5)W_(0.5)O₄//(Oleylamine)_(0.10)/(Oleic Acid)_(0.06)//Air 220°C.

NiMo_(0.5)W_(0.5)O₄ was prepared as described in Comparative Example 1.After it was dried and calcined at about 300° C., it was composited withan inert binder into bound particles, such that about 7 wt % of theweight of the bound particles was the inert binder (with the remainderbeing the mixed metal oxide). About 6.48 g of oleylamine (70% technicalgrade, commercially available from Aldrich of Milwaukee, Wis.) was mixedtogether with about 3.08 g of oleic acid (90% technical grade,commercially available from Aldrich of Milwaukee, Wis.) and heated toabout 100° C. to form a solution. About 50 grams of the bound particlesof NiMo_(0.5)W_(0.5)O₄ were likewise heated to about 100° C., and thenthe solution was used to simultaneously co-impregnate the organiccomponents into/onto the bound particles. The resultant catalyst had anapproximate composition of NiMo_(0.5)W_(0.5)O₄(oleylamine)_(0.10)(oleicacid)_(0.06). This impregnated sample was dried in a drying furnaceovernight at about 100° C., placed in a box furnace, heated in air atabout 0.5° C./min up to about 220° C., and held for about four hours atthat temperature. The heat treated sample was then cooled toambient/room temperature and removed from the furnace (labeled ascatalyst P). This sample was compared against the NiMo_(0.5)W_(0.5)O₄described in Comparative Example 1, which was calcined at about 300° C.and formed into particles by compositing with an inert binder into boundparticles, such that about 7 wt % of the weight of the bound particleswas the inert binder (with the remainder being the mixed metal oxide),but which bound particles were not subjected to organic impregnation(labeled as catalyst N).

Both catalyst samples N and P were sulfided using a procedure similar tothat described in Example 20 herein. Upon sulfiding, the catalystsamples were each contacted with the same VGO feed from Table 11 hereinin the same manner as in Example 20 at the following conditions: atemperature of about 365° C., a total pressure of about 1200 psig (about8.3 MPag), a hydrogen treat gas rate of about 5000 scf/bbl (about 845Sm³/m³), and a weight hourly space velocity (WHSV) of about 1.1 hr⁻¹.The HDN and HDS capability of these catalyst samples were compared afterabout 13 days on stream. The nitrogen and sulfur contents were obtainedand are shown in Table 29 below.

TABLE 29 Catalyst Days on stream N content [wppm] S content [wppm] N 13310 320 P 13 172 138

Example 35 Preparation of NiWO₄//(Ethanolamine)₁/(CitricAcid)_(0.33)//Air 220° C.

NiWO₄ was prepared as described in Comparative Example 1 and was driedand calcined at about 300° C. About 20 grams of the calcined NiWO₄powder was impregnated with about 3.98 grams of ethanolamine using anincipient wetness technique. The impregnated powder was dried about 100°C. overnight and then cooled to ambient/room temperature. Thereafter, anaqueous solution (˜4 mL) containing about 4.18 grams of citric acid wasimpregnated into/onto the ethanolamine-impregnated powder to theincipient wetness point. This sequentially impregnated sample was driedin a drying furnace overnight at about 100° C., placed in a box furnace,heated in air at about 0.5° C./min up to about 220° C., and held forabout four hours at that temperature. The heat treated sample was thencooled to ambient/room temperature and removed from the furnace (labeledas catalyst Q). This sample was compared against the NiWO₄ andNiMo_(0.5)W_(0.5)O₄ samples described in Comparative Example 1, whichwere calcined at about 300° C., but which were not subjected to organicimpregnation (catalysts A and B, respectively).

Catalyst samples Q and B were sulfided using a procedure similar to thatdescribed in Example 20 herein. Upon sulfiding, the catalyst sampleswere each contacted with the same VGO feed from Table 11 herein in thesame manner as in Example 20 at the following conditions: a temperatureof about 365° C., a total pressure of about 1200 psig (about 8.3 MPag),a hydrogen treat gas rate of about 5000 scf/bbl (about 845 Sm³/m³), anda weight hourly space velocity (WHSV) of about 1.1 hr⁻¹. The HDN and HDScapability of these catalyst samples were compared after about 26 dayson stream. The nitrogen and sulfur contents for catalysts Q and B wereobtained and are shown in Table 30 below.

TABLE 30 Catalyst Days on stream N content [wppm] S content [wppm] Q 26295 300 B 26 298 292

Unsulfided versions of catalyst samples Q, A, B, and F(NiMo_(0.5)W_(0.5)O₄//(oleylamine)_(0.13)/(citric acid)_(0.15)//air 220°C.—Example 21) were analyzed using XRD techniques (FIG. 14). The XRDpeak between about 8° and 18° two-theta is believed to represent the(002) crystalline reflection, which correlates to the sulfided Group 6metal stack height in these samples. It is noteworthy that catalystsamples A and B (no organic treatment) exhibit relatively narrow andintense peaks, corresponding to stack heights of at least 4, whereascatalyst samples Q and F exhibit broader and less intense peaks,corresponding to stack heights of about 2.1 and 2.2, respectively.

Example 36 Effect of Organic Treatment Temperature on NiW Catalysts

NiWO₄ was prepared as described in Comparative Example 1. After it wasdried and calcined at about 300° C., it was composited with an inertbinder into bound particles, such that about 7 wt % of the weight of thebound particles was the inert binder (with the remainder being the mixedmetal oxide). Oleylamine (70% technical grade, commercially availablefrom Aldrich of Milwaukee, Wis.) was mixed together with oleic acid (90%technical grade, commercially available from Aldrich of Milwaukee, Wis.)and heated to about 100° C. to form a solution. Three samples of thebound particles of NiWO₄ were likewise heated to about 100° C., and thenan amount of the solution was used to simultaneously co-impregnate theorganic components into/onto each of the samples of bound particles, theamount being sufficient to attain a mole ratio of NiWO₄ to oleylamine ofabout 1:0.10 and to attain a mole ratio of NiWO₄ to oleic acid of about1:0.06. The resultant catalysts thus had an approximate composition ofNiWO₄//(oleylamine)_(0.1)/(oleic acid)_(0.06). These impregnated sampleswere each dried in air in a drying furnace overnight at about 100° C.One of the three samples was cooled to ambient/room temperature andstored without further treatment (labeled as catalyst R). Another of thethree samples was then placed in a box furnace, heated in air at about0.5° C./min up to about 230° C., and held for about 4 hours at thattemperature. The high-temperature sample was then cooled to ambient/roomtemperature and removed from the furnace (labeled as catalyst S). Thelast of the three samples was then treated in a flowing nitrogen stream(about 200 cm³/min) in a quartz line tube furnace, with a heating rateof about 2° C./min, to a final temperature of about 230° C. and held atthat temperature for about 90 minutes. It was then cooled toambient/room temperature and removed from the furnace (labeled ascatalyst T).

Catalysts R, S, and T were subsequently analyzed by solid state ¹³C NMR.For these analyses, the ¹³C MAS NMR spectra were recorded atambient/room temperature (about 20-25° C.) on a ˜9.4 T VarianInfinityPlus 400 spectrometer corresponding to a ¹³C Larmor frequency of˜100.4 MHz using a ˜4 mm (o.d.) MAS spinning probe at about 14 kHz, ˜4μsec π/2 pulses with ¹H decoupling during data acquisition, a pulsedelay of ˜60 sec, and about 436-1536 transients were collected. The ¹³CNMR spectra were referenced against tetramethylsilane (δ_(C)≈0.0 ppm),using hexamethylbenzene as a secondary external standard and setting themethyl peak at 17.36 ppm. The spectra for these three catalysts areshown in FIG. 15 (R at top, S in middle, and T at bottom). All NMR datawere recorded using Varian Inc.'s Spinsight™ NMR data acquisitionsoftware and all processing was done using NutsPro™ (NMR UtilityTransform Software—Professional) software package from Acorn NMR, Inc.The free induction decays (FIDs) were Fourier transformed, phased, andbaseline correction done using a subroutine which fits the baseline witha 5th order polynomial. The relative amounts of the unsaturated carbonwere determined by comparing the integrated area of the peaks attributedto unsaturated and aromatic carbons (δ_(c) extending from about 160 ppmto about 90 ppm) to the sum of the integrated areas attributed to theunsaturated and aromatic carbons plus the aliphatic/saturated carbons(sum of main aliphatic/saturated peak at δ_(c) extending from about 80ppm to about 10 ppm plus the corresponding aliphatic/saturated sidebandsat δ_(c) extending from about 200 ppm to 160 ppm and at δ_(c) extendingfrom about −90 ppm to about −130 ppm). No spinning sideband intensitywas detected for the unsaturated/aromatic carbons (if present, theywould appear at δ_(c) ˜250 ppm and δ_(c) ˜−20 ppm, respectively). Theresults based on the NMR data is shown in Table 31 below.

TABLE 31 Unsaturated Total % Unsaturated Catalyst Treatment/Tempintegration integration Carbons R Air/100° C. 100 359.7 27.8 S Air/230°C. 75.3 221.9 33.9 T N₂/230° C. 27.3 81.9 33.3

Based on this quantitative NMR data, increased unsaturation level canstem from thermal treatment of the organics at temperatures above 100°C. This NMR technique could not differentiate isolated or conjugatedcarbon-carbon unsaturations from aromatic unsaturations, and the percentunsaturated carbon value represents both aromatic and non-aromaticunsaturated carbons. Without being bound by theory, it is postulatedthat additional unsaturated carbons resulting from thermal treatment ofthe organics can cause an increase in observable catalytic HDN activity.

To test the idea of increased catalytic HDN activity for catalystshaving additional unsaturations from organic treatment, catalysts R andS were sulfided using a procedure similar to that described in Example20 herein. Upon sulfiding, the catalyst samples were each contacted witha VGO feed having the properties listed in Table 32 below in the samemanner and under the same conditions as in Example 35.

TABLE 32 Gravity, API ~21.6 Sulfur, wt % ~1.72 Nitrogen, wppm ~1684Basic Nitrogen, wppm ~510 Hydrogen, wt % ~12.15 Nickel, wppm ~0.5Vanadium, wppm ~2.4 GC Distillation (wt %), ° C. IBP ~2l6  5 ~311 10~344 20 ~385 30 ~414 40 ~435 50 ~455 60 ~474 70 ~496 80 ~519 90 ~549 95~572 FBP ~621 Saturates, wt % ~41.4 1-Ring Aromatics, wt % ~17 2-RingAromatics, wt % ~16.3 3-Ring Aromatics, wt % ~11.5 4-Ring Aromatics, wt% ~4.7 Polars, wt % ~1.2

The HDN and HDS capability of these catalyst samples were compared afterabout 21 days on stream. The nitrogen contents for products achievedusing catalysts R and S under these conditions were obtained and areshown in Table 33 below. These results indicate the much improved HDNactivity of catalyst organically treated above 100° C.

TABLE 33 Catalyst Days on stream N content [wppm] RVA RMA R 21 472 0.981.02 S 21 216 1.61 1.60

Example 37 Effect of Organic Treatment Environment on NiW Catalysts

For this experiment, two samples were prepared ofNiWO₄//(oleylamine)_(0.13)/(citric acid)_(0.15). The NiWO₄ was preparedas described in Comparative Example 1, followed by drying andcalcination at about 300° C., and then cooling to ambient/roomtemperature. Oleylamine (70% technical grade, commercially availablefrom Aldrich of Milwaukee, Wis.) was mixed together with an aqueoussolution of citric acid and heated to about 100° C. to form a solution.Both samples of calcined NiWO₄ were likewise heated to about 100° C.,and then an amount of the solution was used to simultaneouslyco-impregnate the organic components into/onto each sample, the amountbeing sufficient to attain a mole ratio of NiWO₄ to oleylamine of about1:0.13 and to attain a mole ratio of NiWO₄ to citric acid of about1:0.15. These impregnated samples were each dried in a drying furnaceovernight at about 100° C. and then prepared for infrared analysis.

Transmission infrared spectra characterizing the samples were collectedusing a Thermo Scientific Nicolet 6700 FT-IR spectrometer equipped witha MCT detector and are shown in FIGS. 16A-B. About 0.012 to 0.016 g ofeach sample were mixed with about 0.04 g of diamond powder and pressedinto self-supporting wafers that were loaded into an IR cell connectedto a vacuum/adsorption system, which allowed recording of spectra whilethe treatment gases flowed through and around the wafer during infraredcharacterization. The IR spectra were collected, processed and analyzedwith Thermo Scientific Omnic V7.1 software. Each reported spectrum isthe average of about 256 scans across the range front about 4000 cm⁻¹ toabout 1000 cm⁻¹, with a spectral resolution of about 4 cm⁻¹. Thereported spectra were each normalized by subtracting a backgroundspectrum of an empty IR cell. Peak deconvolution and fitting analysiswas done using symmetric Gaussian functions in the 2000-1200 cm⁻¹ regionwith Omnic V7.1 commercial software, though other commercial software,such as OriginLab or PeakFit, could have alternately been used.

The first sample was placed in an IR cell and subject to a flow of ˜20vol % oxygen in helium (oxidative environment) at about 100° C. forabout 90 minutes, at which time a transmission IR spectrum was collected(FIG. 16A-1, dashed line). Immediately thereafter, that same sample wassubject to a flow of ˜20 vol % oxygen in helium (oxidative environment)at about 230° C. for about 240 minutes, at which time another spectrumwas collected (FIG. 16A-2, solid line). The second sample was placed inan IR cell and subject to a flow of ˜100% helium (non-oxidativeenvironment) at about 100° C. for about 90 minutes, at which time atransmission IR spectrum was collected (FIG. 16B-3, dashed line)Immediately thereafter, that same sample was subject to a flow of ˜100%helium (non-oxidative environment) at about 230° C. for about 240minutes, at which time another spectrum was collected (FIG. 16B-4 solidline).

Regarding the spectra in FIG. 16A, of particular interest on spectrum(2) were infrared bands centered at maxima of about 1773 cm⁻¹ and about1715 cm⁻¹, along with two broad bands centered in the ˜1570-1620 cm⁻¹and ˜1380-1450 cm⁻¹ regions. The fitting analysis of the sample treatedin the higher-temperature oxidative environment (2) identified a peakextending from about 1618 cm⁻¹ to about 1812 cm⁻¹ and centered at about1715 cm⁻¹ with a height of about 0.40 a.u., a full width at half maximum(FWHM) of about 63 cm⁻¹, and an integrated area of about 27.0 a.u. Thefeature centered at about 1773 cm⁻¹ was fitted with a peak extendingfrom about 1723 cm⁻¹ to about 1841 cm⁻¹ with a height of about 0.16a.u., a FWHM of about 51 cm⁻¹, and an integrated area of about 8.66 a.u.The most prominent peak identified at lower wavenumbers extended fromabout 1290 cm⁻¹ to about 1512 cm⁻¹ and was centered at about 1400 cm⁻¹with a height of about 0.12 a.u., a FWHM of about 81 cm⁻¹, and anintegrated area of about 9.98 a.u. In contrast, the fitting analysis ofthe sample treated in the lower-temperature oxidative environment (1)identified a peak extending from about 1626 cm⁻¹ to about 1816 cm⁻¹ andcentered at about 1722 cm⁻¹ with a height of about 0.26 a.u., a FWHM ofabout 66 cm⁻¹, and an integrated area of about 18.1a.u. The peakcentered at about 1395 cm⁻¹ (ranging from about 1310 cm⁻¹ to about 1440cm⁻¹) had a height of about 0.30 a.u., a FWHM of about 110 cm⁻¹, and anintegrated area of about 34.8 a.u. No peak was identified in the regionaround 1773 cm⁻¹ for this sample. For the sample treated in thehigher-temperature oxidative environment (2), the ratio of the heightand integrated area of the peak centered at about 1715 cm⁻¹, compared tothe one centered at about 1400 cm⁻¹, was about 3.5 and about 2.7,respectively. In comparison, for the sample treated in thelower-temperature oxidative environment (1), the ratio of the height andintegrated area of the peak centered at about 1715 cm⁻¹, compared to theone centered at about 1400 cm⁻¹, was about 0.87 and about 0.52,respectively.

Regarding the spectra in FIG. 16B, of particular interest on spectrum(4) were infrared bands centered at maxima of about 1773 cm⁻¹ and about1698 cm⁻¹, along with broad bands centered in the −4570-1620 cm⁻¹ and˜1380-1450 cm⁻¹ regions. The fitting analysis of the sample treated inthe higher-temperature non-oxidative environment (4) identified a peakextending from about 1653 cm⁻¹ to about 1765 cm⁻¹ and centered at about1706 cm⁻¹ with a height of about 0.15 a.u., a FWHM of about 39 cm⁻¹, andan integrated area of about 6.17 a.u. The feature centered at about 1671cm⁻¹ was fitted with a peak extending from about 1582 cm⁻¹ to about 1761cm⁻¹ with a height of about 0.17 a.u., a FWHM of about 64 cm⁻¹, and anintegrated area of about 11.6 a.u. The most prominent peak identified atlower wavenumbers extended from about 1416 cm⁻¹ to about 1495 cm⁻¹ andwas centered at about 1455 cm⁻¹ with a height of about 0.11a.u., a FWHMof about 29 cm⁻¹, and an integrated area of about 3.31a.u. The featuredcentered at about 1410 cm⁻¹ was fitted with a peak extending from about1324 cm⁻¹ to about 1482 cm⁻¹ with a height of about 0.10 a.u., a FWHM ofabout 62 cm⁻¹, and an integrated area of about 6.85 a.u. In contrast,the fitting analysis of the sample treated in the lower-temperaturenon-oxidative environment (3) identified a peak extending from about1630 cm⁻¹ to about 1815 cm⁻¹ and centered at about 1723 cm⁻¹ with aheight of about 0.17 a.u., a FWHM of about 66 cm⁻¹, and an integratedarea of about 11.81a.u. The peak centered at about 1415 cm⁻¹ (rangingfrom about 1284 cm⁻¹ to about 1540 cm⁻¹) had a height of about 0.14, aFWHM of about 95 cm⁻¹, and an integrated area of about 14.27 a.u. Nopeak was identified in the region around 1773 cm⁻¹ for that spectrum.For the sample treated in the higher-temperature non-oxidativeenvironment (4), the ratio of the height and integrated area of the peakcentered at about 1715 cm⁻¹, compared to the one centered at about 1410cm⁻¹, was about 1.4 and about 0.9, respectively. In comparison, for thesample treated in the lower-temperature non-oxidative environment (3),the ratio of the height and integrated area of the peak centered atabout 1715 cm⁻¹, compared to the one centered at about 1410 cm⁻¹, wasabout 1.2 and about 0.8, respectively.

Although the peaks in these spectra have been identified herein by theirwavenumber (cm⁻¹), those peaks can be correlated to specific bondexcitations (stretches, wags, bends, etc.), based on various factorsincluding (but not necessarily limited to) the wavenumber position ofpeaks and the physico-chemical nature of bonds known or presumed toexist within each sample. Without being bound by theory, in the infraredspectra described herein, the peaks centered at about 1773 cm⁻¹ and atabout 1715 cm⁻¹ were presumptively assigned to C═O stretching inaldehyde-type carbonyl bonds and C═C stretching in non-aromaticunsaturated hydrocarbon bonds, respectively. The broad feature centeredat around 1380-1450 cm⁻¹ was presumptively assigned to a combination ofinfrared bands from C═C stretching in aromatic rings, and the broadfeature centered at about 1570-1620 cm⁻¹ was presumptively assigned to acombination of infrared bands from C═C stretching in aromatic rings andC═C stretching in non-aromatic unsaturated hydrocarbons. Based on theapproximate intensities of the infrared peaks described above, theconcentration of non-aromatic unsaturated hydrocarbons observed by IRspectroscopy appears to be somewhat higher than that of aromatichydrocarbons in the sample treated in the higher-temperature oxidativeenvironment, compared to the sample treated in the higher-temperaturenon-oxidative environment.

Example 38 Equimolar Amount of First and Second Organic Compounds

Two samples of NiWO₄ were prepared as described in Comparative Example1, followed by drying and calcination of each at about 300° C., and thencooling to ambient/room temperature. For the equimolar oleylamine-oleicacid sample, oleylamine (70% technical grade, commercially availablefrom Aldrich of Milwaukee, Wis.) was mixed together with oleic acid (90%technical grade, commercially available from Aldrich of Milwaukee, Wis.)at ambient/room temperature to form a solution. One sample of calcinedNiWO₄ at ambient/room temperature was exposed to an amount of theoleylamine-oleic acid solution to simultaneously co-impregnate theorganic components into/onto the sample, the amount being sufficient toattain a mole ratio of NiWO₄ to oleylamine of about 1:0.074 and toattain a mole ratio of NiWO₄ to oleic acid of about 1:0.094. For theequimolar oleylamine-citric acid sample, the other sample of calcinedNiWO₄ at ambient/room temperature was impregnated first with oleylamine(70% technical grade, commercially available from Aldrich of Milwaukee,Wis.), such that the mole ratio of NiWO₄ to oleylamine was about 1:0.11.The sample was placed into a drying oven and maintained at about 100° C.overnight and cooled to ambient/room temperature. The dried sample wasthen impregnated with an aqueous citric acid solution, such that theNiWO₄ to citric acid mole ratio was about 1:0.15. Although the nominalmolar ratios do not appear on their face to be equimolar, it should benoted that, once they are adjusted for their respective purities (e.g.,70% oleylamine, 90% oleic acid, etc.), the actual molar ratios areapproximately equimolar.

Both samples were then dried at about 100° C. overnight in a dryingfurnace and were subsequently placed in a box furnace (in air) andheated at a rate of about 0.5° C./min to a final temperature of about220° C. Both samples were held at that temperature for about 4 hours andwere then cooled to ambient/room temperature and removed from thefurnace. The equimolar oleylamine-oleic acid sample was labeledOLE_(EQ), and the equimolar oleylamine-citric acid sample was labeledCIT_(EQ). The equimolar samples were compared against a referencecatalyst (B) that was not treated with any organics. These samples werethen sulfided and tested for catalytic HDN activity through contactingwith a VGO feed having the properties listed in Table 32 above in thesame manner and under the same conditions as in Example 36. The results,including the HDN activities on a relative volume basis (i.e., RVAs) andon a relative molar basis (i.e., RMAs), are shown in Table 34 below.

TABLE 34 Catalyst Days on stream N content [wppm] RVA RMA OLE_(EQ) 12114 1.71 1.58 CIT_(EQ) 12 107 1.75 1.54 B 12 344 1.00 1.00

It is noted that the samples containing equimolar quantities of thefirst and second organic compounds show distinct improvement, though notas profound an improvement as the samples in which the amine-containingorganic compound is present in a molar excess to the carboxylicacid-containing organic compound.

Example 39 Effect of Reducing Content of Group 8-10 Metal

A first sample containing equimolar amounts of nickel and tungsten(NiWO₄) was prepared according to Comparative Example 1. After it wasdried and calcined at about 300° C., it was composited with an inertbinder and formed into an extrudate having an average diameter of about1.3 mm, such that about 7 wt % of the weight of the extrudate was theinert binder (with the remainder being the mixed metal oxide).Oleylamine (70% technical grade, commercially available from Aldrich ofMilwaukee, Wis.) was mixed together with oleic acid (90% technicalgrade, commercially available from Aldrich of Milwaukee, Wis.) andheated to about 100° C. to form a solution. The first sample of calcinedequimolar NiWO₄ was likewise heated to about 100° C., and then an amountof the solution was used to simultaneously co-impregnate the organiccomponents into/onto the sample, the amount being sufficient to attain amole ratio of NiWO₄ to oleylamine of about 1:0.10 and to attain a moleratio of NiWO₄ to oleic acid of about 1:0.06. This impregnated samplewas dried in air in a drying furnace overnight at about 100° C. Thesample was then placed in a box furnace, heated in air at about 0.5°C./min up to about 230° C., and held for about 4 hours at thattemperature. This sample was then cooled to ambient/room temperature andremoved from the furnace (labeled as catalyst AA).

A second sample was prepared using a similar procedure to ComparativeExample 1, but adjusting the ingredients to provide a nickel-to-tungstenmolar ratio of only about 0.75:1. After it was dried, calcined at about300° C., and then cooled to ambient/room temperature, an XRD spectrumwas taken (not shown), which appeared to have features roughly similarto the equimolar nickel-tungsten oxide, as calcined. Oleylamine (70%technical grade, commercially available from Aldrich of Milwaukee, Wis.)was mixed together with oleic acid (90% technical grade, commerciallyavailable from Aldrich of Milwaukee, Wis.) and heated to about 100° C.to form a solution. The second sample of calcined Ni_(0.75)WO_(3.75) waslikewise heated to about 100° C., and then an amount of the solution wasused to simultaneously co-impregnate the organic components into/ontothe sample, the amount being sufficient to attain a mole ratio ofNi_(0.75)WO_(3.75) to oleylamine of about 1:0.10 and to attain a moleratio of Ni_(0.75)WO_(3.75) to oleic acid of about 1:0.06. Thisimpregnated sample was dried in air in a drying furnace overnight atabout 100° C. The sample was then placed in a box furnace, heated in airat about 0.5° C./min up to about 220° C., and held for about 4 hours atthat temperature. This sample was then cooled to ambient/roomtemperature and removed from the furnace (labeled as catalyst Y).

A third sample was prepared using a similar procedure to ComparativeExample 1, but adjusting the ingredients to provide a nickel-to-tungstenmolar ratio of only about 0.5:1. After it was dried, calcined at about300° C., and then cooled to ambient/room temperature, an XRD spectrumwas taken (not shown), which appeared to have several different featuresfrom the calcined first and second samples, including (but not limitedto) sharper [002] stacking peak and a collection of peaks more analogousto a heteropoly phase configuration than to a typical hexagonal nickeltungstate. Oleylamine (70% technical grade, commercially available fromAldrich of Milwaukee, Wis.) was mixed together with oleic acid (90%technical grade, commercially available from Aldrich of Milwaukee, Wis.)and heated to about 100° C. to form a solution. The second sample ofcalcined Ni_(0.5)WO_(3.5) was likewise heated to about 100° C., and thenan amount of the solution was used to simultaneously co-impregnate theorganic components into/onto the sample, the amount being sufficient toattain a mole ratio of Ni_(0.5)WO_(3.5) to oleylamine of about 1:0.10and to attain a mole ratio of Ni_(0.5)WO_(3.5) to oleic acid of about1:0.06. This impregnated sample was dried in air in a drying furnaceovernight at about 100° C. The sample was then placed in a box furnace,heated in air at about 0.5° C./min up to about 220° C., and held forabout 4 hours at that temperature. This sample was then cooled toambient/room temperature and removed from the furnace (labeled ascatalyst Z).

A fourth sample was prepared using a similar procedure to ComparativeExample 1, but adjusting the ingredients to provide a nickel-to-tungstenmolar ratio of about 1.2:1, followed by drying, calcination at about300° C., and then cooling to ambient/room temperature. Oleylamine (70%technical grade, commercially available from Aldrich of Milwaukee, Wis.)was mixed together with oleic acid (90% technical grade, commerciallyavailable from Aldrich of Milwaukee, Wis.) and heated to about 100° C.to form a solution. The second sample of calcined Ni_(1.2)WO_(4.2) waslikewise heated to about 100° C., and then an amount of the solution wasused to simultaneously co-impregnate the organic components into/ontothe sample, the amount being sufficient to attain a mole ratio ofNi_(1.2)WO_(4.2) to oleylamine of about 1:0.10 and to attain a moleratio of Ni_(1.2)WO_(4.2) to oleic acid of about 1:0.06. Thisimpregnated sample was dried in air in a drying furnace overnight atabout 100° C. The sample was then placed in a box furnace, heated in airat about 0.5° C./min up to about 220° C., and held for about 4 hours atthat temperature. This sample was then cooled to ambient/roomtemperature and removed from the furnace (labeled as catalyst X).

These samples were compared against a reference catalyst (B) that wasnot treated with any organics. All these samples were then sulfided andtested for catalytic HDN activity through contacting with a VGO feedhaving the properties listed in Table 32 above in the same manner andunder the same conditions as in Example 36. The results, including theHDN activities on a relative volume basis (i.e., RVAs) and on a relativemolar basis (i.e., RMAs), are shown in Table 35 below.

TABLE 35 Catalyst Days on stream N content [wppm] RVA RMA X 26 141 1.441.76 AA 27 108 1.64 1.70 Y 27 155 1.42 1.20 Z 27 256 1.12 0.87 B 28 3111.00 1.00

It is noted that, in these experiments, the HDN activity of the 0.75Ni:W ratio catalyst still exhibited a modest increase, on a molar basis,due to the dual organic treatment, while the HDN activity of the 0.5Ni:W ratio catalyst showed a decrease, on a molar basis, despite thedual organic treatment. Nevertheless, the equimolar Ni:W catalyst andthe catalyst having an Ni:W ratio greater than 1 showed 70% or greaterrelative molar HDN activity. Thus, Ni:W ratios at or above 0.75 seem tobe desirable, with about equimolar to somewhat above equimolar Ni:Wratios appearing to be particularly desirable on a relative molaractivity basis.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For this reason, then, reference shouldbe made solely to the appended claims for purposes of determining thetrue scope of the present invention.

What is claimed is:
 1. A bulk mixed metal catalyst precursor compositionproduced by heating a composition comprising one metal from Group 6 ofthe Periodic Table of the Elements, at least one metal from Groups 8-10of the Periodic Table of the Elements, and a reaction product formedfrom (i) a first organic compound containing at least one amine groupand at least 10 carbon atoms or (ii) a second organic compoundcontaining at least one carboxylic acid group and at least 10 carbonatoms, but not both (i) and (ii), wherein the reaction product containsadditional unsaturated carbon atoms, relative to (i) the first organiccompound or (ii) the second organic compound, wherein the metals of thecatalyst precursor composition are arranged in a crystal lattice, andwherein the reaction product is not located within the crystal lattice,to a temperature from about 195° C. to about 250° C. for a timesufficient for the first or second organic compounds to form a reactionproduct in situ that contains unsaturated carbon atoms not present inthe first or second organic compounds.
 2. A bulk mixed metalhydroprocessing catalyst composition produced by sulfiding the catalystprecursor composition of claim
 1. 3. The catalyst precursor compositionof claim 1, wherein one or more of the following are satisfied: thecatalyst precursor composition exhibits a content of unsaturated carbonatoms, as measured according to peak area comparisons using ¹³C NMRtechniques, of at least 29%; the catalyst precursor composition exhibitsan increase in content of unsaturated carbon atoms, as measuredaccording to peak area comparisons using ¹³C NMR techniques, of at leastabout 17%, compared to a collective content of unsaturated carbon atomspresent in the first or second organic compound; the catalyst precursorcomposition exhibits a ratio of unsaturated carbon atoms to aromaticcarbon atoms, as measured according to peak area ratios using infraredspectroscopic techniques of a deconvoluted peak centered from about 1700cm-1 to about 1730 cm-1, compared to a deconvoluted peak centered fromabout 1380 cm⁻¹ to about 1450 cm⁻¹, of at least 0.9; and the catalystprecursor composition exhibits a ratio of unsaturated carbon atoms toaromatic carbon atoms, as measured according to peak area ratios usinginfrared spectroscopic techniques of a deconvoluted peak centered fromabout 1700 cm⁻¹ to about 1730 cm⁻¹, compared to a deconvoluted peakcentered from about 1380 cm⁻¹ to about 1450 cm⁻¹, of up to
 15. 4. Thebulk mixed metal catalyst precursor of claim 2, wherein one or more ofthe following are satisfied: the sulfided bulk mixed metal catalystprecursor exhibits a layered structure comprising a plurality of stackedlayers of sulfided Group 6 metal, such that the average number ofstacked layers is from about 1.5 to about 3.5; the sulfided bulk mixedmetal catalyst precursor exhibits a layered structure comprising aplurality of stacked layers of sulfided Group 6 metal, such that theaverage number of stacked layers is at least about 0.8 stacked layersless than an identical sulfided bulk mixed metal catalyst precursor thathas not been treated using first or second organic compounds; uponexposure of the sulfided bulk mixed metal catalyst precursor to a vacuumgasoil feedstock under hydroprocessing conditions, the sulfided bulkmixed metal catalyst precursor exhibits a hydrodenitrogenation RMA of atleast 57% greater than a sulfided catalyst composition that has not beentreated using first or second organic compounds; upon exposure of thesulfided bulk mixed metal catalyst precursor to a vacuum gasoilfeedstock under hydroprocessing conditions, the sulfided bulk mixedmetal catalyst precursor exhibits a hydrodenitrogenation RMA of up to500% greater than a sulfided catalyst composition that has not beentreated using first or second organic compounds; upon exposure of thesulfided bulk mixed metal catalyst precursor to a vacuum gasoilfeedstock under hydroprocessing conditions, the sulfided bulk mixedmetal catalyst precursor exhibits a hydrodenitrogenation RMA at least30% greater than a sulfided catalyst composition that has been treatedwith only a single organic compound having less than 10 carbon atoms;and upon exposure of the sulfided bulk mixed metal catalyst precursor toa vacuum gasoil feedstock under hydroprocessing conditions, the sulfidedbulk mixed metal catalyst precursor exhibits a hydrodenitrogenation RMAup to 500% greater than a sulfided catalyst composition that has beentreated with only a single organic compound having less than 10 carbonatoms.
 5. A bulk mixed metal catalyst precursor composition according toclaim 1 in which the metal from Group 6 of the Periodic Table of theElements is tungsten.
 6. A bulk mixed metal catalyst precursorcomposition according to claim 5 comprising one metal from Group 8 ofthe Periodic Table of the Elements.
 7. A bulk mixed metal catalystprecursor composition according to claim 6 in which the metal from Group8 of the Periodic Table of the Elements is nickel.
 8. A bulk mixed metalcatalyst precursor composition according to claim 1 in which thecomposition comprising the metals from Group 6 and Groups 8-10 of thePeriodic Table of the Elements, and the reaction product containingadditional unsaturated carbon atoms is formed from the first or secondorganic compounds by heating to a temperature from about 195° C. toabout 250° C. in an oxidizing atmosphere.
 9. A bulk mixed metalhydroprocessing catalyst composition produced by sulfiding the catalystprecursor composition of claim
 8. 10. A process for producing a catalystprecursor composition containing in situ-formed unsaturated carbonatoms, the process comprising: (a) treating a catalyst precursorcomposition comprising one metal from Group 6 of the Periodic Table ofthe Elements, at least one metal from Groups 8-10 of the Periodic Tableof the Elements, with a first organic compound containing at least oneamine group and at least 10 carbons or a second organic compoundcontaining at least one carboxylic acid group and at least 10 carbons,to form an organically treated precursor catalyst composition; and (b)heating said organically treated precursor catalyst composition at atemperature from about 195° C. to about 250° C. for a time sufficientfor the first or second organic compounds to react to form additional insitu unsaturated carbon atoms not present in the first or second organiccompounds, but not for so long that more than 50% by weight of the firstor second organic compound is volatilized, thereby forming a catalystprecursor composition containing in situ formed unsaturated carbonatoms.
 11. The process of claim 10, wherein said one metal from Group 6is Mo or W, and wherein said at least one metal from Groups 8-10 is Co,Ni, or a combination thereof.
 12. The process of claim 10, wherein saidfirst organic compound comprises a primary monoamine having from 10 to30 carbon atoms or said second organic compound comprises only onecarboxylic acid group and has from 10 to 30 carbon atoms.
 13. Theprocess of claim 10, wherein the catalyst precursor compositioncontaining in situ formed unsaturated carbon atoms is a bulk metalhydroprocessing catalyst precursor composition consisting essentially ofthe reaction product of the first organic compound or the second organiccompound, an oxide form of the one metal from Group 6, an oxide form ofthe at least one metal from Groups 8-10, and optionally about 20 wt % orless of a binder.
 14. A process for producing a sulfided hydroprocessingcatalyst composition, comprising sulfiding the catalyst precursorcomposition containing in situ formed unsaturated carbon atoms madeaccording to the process of claim 10 under conditions sufficient toproduce the sulfided hydroprocessing catalyst composition.
 15. A processfor producing a sulfided hydroprocessing catalyst composition,comprising sulfiding the catalyst precursor composition containing insitu formed unsaturated carbon atoms made according to the process ofclaim 13 under conditions sufficient to produce the sulfidedhydroprocessing catalyst composition.
 16. A catalyst precursorcomposition containing in situ formed unsaturated carbon atoms madeaccording to the process of claim
 10. 17. A sulfided hydroprocessingcatalyst composition made according to the process of claim
 15. 18. Theprocess of claim 10, wherein one or more of the following are satisfied:the catalyst precursor composition exhibits a content of unsaturatedcarbon atoms, as measured according to peak area comparisons using 13CNMR techniques, of at least 29%; the catalyst precursor compositionexhibits an increase in content of unsaturated carbon atoms, as measuredaccording to peak area comparisons using 13C NMR techniques, of at leastabout 17%, compared to a collective content of unsaturated carbon atomspresent in the first or second organic compound; the catalyst precursorcomposition exhibits a ratio of unsaturated carbon atoms to aromaticcarbon atoms, as measured according to peak area ratios using infraredspectroscopic techniques of a deconvoluted peak centered from about 1700cm⁻¹ to about 1730 cm⁻¹, compared to a deconvoluted peak centered fromabout 1380 cm⁻¹ to about 1450 cm⁻¹, of at least 0.9; and the catalystprecursor composition exhibits a ratio of unsaturated carbon atoms toaromatic carbon atoms, as measured according to peak area ratios usinginfrared spectroscopic techniques of a deconvoluted peak centered fromabout 1700 cm⁻¹ to about 1730 cm⁻¹, compared to a deconvoluted peakcentered from about 1380 cm⁻¹ to about 1450 cm⁻¹, of up to
 15. 19. Aprocess for producing a sulfided hydroprocessing catalyst composition,comprising sulfiding the catalyst precursor composition made accordingto the process of claim 10 under conditions sufficient to produce thesulfided hydroprocessing catalyst composition, wherein one or more ofthe following are satisfied: the sulfided hydroprocessing catalystcomposition exhibits a layered structure comprising a plurality ofstacked layers of sulfided Group 6 metal, such that the average numberof stacked layers is from about 1.5 to about 3.5; the sulfidedhydroprocessing catalyst composition exhibits a layered structurecomprising a plurality of stacked layers of sulfided Group 6 metal, suchthat the average number of stacked layers is at least about 0.8 stackedlayers less than an identical sulfided hydroprocessing catalystcomposition that has not been treated using first or second organiccompounds; upon exposure of the sulfided hydroprocessing catalystcomposition to a vacuum gasoil feedstock under hydroprocessingconditions, the sulfided hydroprocessing catalyst composition exhibits ahydrodenitrogenation RMA of at least 57% greater than a sulfidedcatalyst composition that has not been treated using first or secondorganic compounds; upon exposure of the sulfided hydroprocessingcatalyst composition to a vacuum gasoil feedstock under hydroprocessingconditions, the sulfided hydroprocessing catalyst composition exhibits ahydrodenitrogenation RMA of up to 500% greater than a sulfided catalystcomposition that has not been treated using first or second organiccompounds; upon exposure of the sulfided hydroprocessing catalystcomposition to a vacuum gasoil feedstock under hydroprocessingconditions, the sulfided hydroprocessing catalyst composition exhibits ahydrodenitrogenation RMA at least 30% greater than a sulfided catalystcomposition that has been treated with only a single organic compoundhaving less than 10 carbon atoms; and upon exposure of the sulfidedhydroprocessing catalyst composition to a vacuum gasoil feedstock underhydroprocessing conditions, the sulfided hydroprocessing catalystcomposition exhibits a hydrodenitrogenation RMA up to 500% greater thana sulfided catalyst composition that has been treated with only a singleorganic compound having less than 10 carbon atoms.
 20. A processaccording to claim 19 in which the heating of the organically treatedprecursor catalyst composition is carried out in an oxidizingatmosphere.
 21. A sulfide hydroprocessing catalyst composition producedby the process of claim 20.